Pesticidally active polycyclic derivatives with sulfur containing substituents

ABSTRACT

Polycyclic derivatives of formula I 
     
       
         
         
             
             
         
       
     
     wherein the substituents are as defined in claim  1,  and the agrochemically acceptable salts salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as insecticides and can be prepared in a manner known per se.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.16/201,408, filed Nov. 27, 2018, which is a continuation application ofU.S. patent application Ser. No. 15/541,786, filed Jul. 6, 2017, whichis a 371 National Stage application of International Application No.PCT/EP2016/050593, filed Jan. 14, 2016, which claims priority toEuropean Patent Application No. 15151643.2, filed Jan. 19, 2015, theentire contents of which are hereby incorporated by reference.

The present invention relates to pesticidally active, in particularinsecticidally active polycyclic derivatives containing sulfursubstituents, to compositions comprising those compounds, and to theiruse for controlling animal pests, including arthropods and in particularinsects or representatives of the order Acarina.

Heterocyclic compounds with pesticidal action are known and described,for example, in WO 2012/086848, WO 2013/018928, WO 2014/142292, WO2015/133603, WO2015/000715 and WO 2015/121136 There have now been foundnovel pesticidally active polycyclic ring derivatives with sulphurcontaining phenyl and pyridyl substituents.

The present invention accordingly relates to compounds of formula I,

wherein

A represents CH, N or the N-oxide;

A₁ is CH, N or the N-oxide;

Q is phenyl which can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl;or

Q is a five- to ten-membered monocyclic or fused bicyclic ring systemlinked via a carbon atom to the ring which contains the group A, saidring system can be aromatic, partially saturated or fully saturated andcontains 1 to 4 hetero atoms selected from the group consisting ofnitrogen, oxygen and sulfur,

with the proviso that each ring system cannot contain more than 2 oxygenatoms and more than 2 sulfur atoms, said five- to ten-membered ringsystem can be mono- to polysubstituted by substituents independentlyselected from the group consisting of halogen, cyano, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄alkylsulfanyl,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, —C(O)C₁-C₄alkyl,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyland —C(O)C₁-C₄haloalkyl; or

Q is a five- to six-membered, aromatic, partially saturated or fullysaturated ring system linked via a nitrogen atom to the ring whichcontains the group A, said ring system can be mono- or polysubstitutedby substituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl; and said ring systemcontains 1, 2 or 3 heteroatoms selected from the group consisting ofnitrogen, oxygen and sulfur,

with the proviso that said ring system cannot contain more than oneoxygen atom and more than one sulfur atom; or

Q is C₃-C₆cycloalkyl, or C₃-C₆cycloalkyl mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,CONH₂, carboxyl, C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl and phenyl,wherein said phenyl can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄haloalkylsulfanyl,C₁-C₄halo-alkylsulfinyl, C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl;or

Q is C₂-C₆alkenyl, or C₂-C₆alkenyl mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl and phenyl, wherein saidphenyl can be mono- or polysubstituted by substituents selected from thegroup consisting of halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl;or

Q is C₂-C₆alkynyl, or C₂-C₆alkynyl mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl, tri(C₁-C₄alkyl)silyl andphenyl, wherein said phenyl can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄halo-alkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyland —C(O)C₁-C₄haloalkyl; or

Q is C₁-C₆alkyl, or C₁-C₆alkyl mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano, C₁-C₄alkyl,C₁-C₄haloalkyl, C₃-C₆cycloalkyl, tri(C₁-C₄alkyl)silyl and phenyl,wherein said phenyl can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄halo-alkylsulfanyl,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl;

X is S, SO or SO₂;

R₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl; or

R₁ is C₃-C₆cycloalkyl-C₁-C₄alkyl mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano andC₁-C₄alkyl; or

R₁ is C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl;

R₂ is halogen, cyano, C₁-C₆haloalkyl or C₁-C₆haloalkyl substituted byone or two substituents selected from the group consisting of hydroxyl,methoxy and cyano; or

R₂ is C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), or —C(O)C₁-C₄haloalkyl; or

R₂ is C₃-C₆cycloalkyl which can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano andC₁-C₄alkyl;

X₁ is NR₅; wherein R₅ is hydrogen, C₁-C₄alkyl, C₂-C₆alkenyl,C₂-C₆alkynyl, C₁-C₄alkoxy-C₁-C₄alkyl or C₃-C₆cycloalkyl; or

X₁ is oxygen or sulfur;

R₃ is hydrogen or C₁-C₂-alkyl;

R₄ is hydrogen, halogen or C₁-C₃haloalkyl;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers of the compounds of formula I.

Compounds of formula I which have at least one basic centre can form,for example, acid addition salts, for example with strong inorganicacids such as mineral acids, for example perchloric acid, sulfuric acid,nitric acid, a phosphorus acid or a hydrohalic acid, with strong organiccarboxylic acids, such as C₁-C₄alkanecarboxylic acids which areunsubstituted or substituted, for example by halogen, for example aceticacid, such as saturated or unsaturated dicarboxylic acids, for exampleoxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid orphthalic acid, such as hydroxycarboxylic acids, for example ascorbicacid, lactic acid, malic acid, tartaric acid or citric acid, or such asbenzoic acid, or with organic sulfonic acids, such as C₁-C₄alkane- orarylsulfonic acids which are unsubstituted or substituted, for exampleby halogen, for example methane- or p-toluenesulfonic acid. Compounds offormula I which have at least one acidic group can form, for example,salts with bases, for example mineral salts such as alkali metal oralkaline earth metal salts, for example sodium, potassium or magnesiumsalts, or salts with ammonia or an organic amine, such as morpholine,piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, forexample ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-,di- or trihydroxy-lower-alkylamine, for example mono-, di- ortriethanolamine.

The alkyl groups occurring in the definitions of the substituents can bestraight-chain or branched and are, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl,hexyl, and their branched isomers. Alkylsulfanyl, alkylsulfinyl,alkylsulfonyl, alkoxy, alkenyl and alkynyl radicals are derived from thealkyl radicals mentioned. The alkenyl and alkynyl groups can be mono- orpolyunsaturated. C₁-di-alkylamino is dimethylamino.

Halogen is generally fluorine, chlorine, bromine or iodine. This alsoapplies, correspondingly, to halogen in combination with other meanings,such as haloalkyl or halophenyl.

Haloalkyl groups preferably have a chain length of from 1 to 6 carbonatoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl,1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and2,2,2-trichloroethyl.

Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy,isobutoxy, sec-butoxy and tert-butoxy and also the isomeric pentyloxyand hexyloxy radicals.

Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl,ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl orisopropoxyethyl.

Alkoxycarbonyl is for example methoxycarbonyl (which isC₁alkoxycarbonyl), ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl,n-butoxycarbonyl, tert-butoxycarbonyl, n-pentoxycarbonyl orhexoxycarbonyl.

Alkylsulfanyl is for example methylsulfanyl, ethylsulfanyl,propylsulfanyl, isopropylsulfanyl, butylsulfanyl, pentylsulfanyl, andhexylsulfanyl.

Alkylsulfinyl is for example methylsulfinyl, ethylsulfinyl,propylsulfinyl, isopropylsulfinyl, a butylsulfinyl, pentylsulfinyl, andhexylsulfinyl.

Alkylsulfonyl is for example methylsulfonyl, ethylsulfonyl,propylsulfonyl, isopropylsulfonyl, butylsulfonyl, pentylsulfonyl, andhexylsulfonyl.

Haloalkylsulfanyl is for example trifluoromethylsulfanyl,2,2,2-trifluoroethylsulfanyl, and pentafluoroethylsulfanyl.

Haloalkylsulfinyl is for example trifluoromethylsulfinyl,2,2,2-trifluoroethylsulfinyl, or pentafluoroethylsulfinyl.

Haloalkylsulfonyl is for example trifluoromethylsulfonyl,2,2,2-trifluoroethylsulfonyl, and pentafluoroethylsulfonyl.

Cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl andcyclohexyl.

In the context of this invention, examples of a five- to six-membered,aromatic, partially saturated or fully saturated ring system that arelinked via a nitrogen atom to the ring which contains the group A, arefor example, pyrazole, pyrrole, pyrrolidine, pyrrolidine-2-one,piperidine, morpholine, imidazole, triazole and pyridine-2-one.

In the context of this invention “mono- to polysubstituted” in thedefinition of the substituents, means typically, depending on thechemical structure of the substituents, monosubstituted to seven-timessubstituted, preferably monosubstituted to five-times substituted, morepreferably mono-, double- or triple-substituted.

The compounds of formula I according to the invention also includehydrates which may be formed during the salt formation.

According to the present invention, a five- to ten-membered monocyclicor fused bicyclic hetero-ring system which can be aromatic, partiallysaturated or fully saturated and contains 1 to 4 hetero atoms selectedfrom the group consisting of nitrogen, oxygen and sulfur, with theproviso that each ring system cannot contain more than 2 oxygen atomsand more than 2 sulfur atoms or a three- to ten-membered, monocyclic orfused bicyclic ring system which may be aromatic, partially saturated orfully saturated is, depending of the number of ring members, preferablyselected from the group consisting of the following heterocyclic groups:

pyrrolyl; pyrazolyl; isoxazolyl; furanyl; thienyl; imidazolyl; oxazolyl;thiazolyl; isothiazolyl; triazolyl; oxadiazolyl; thiadiazolyl;tetrazolyl; furyl; pyridyl; pyrimidyl; pyrazinyl; pyridazinyl;triazinyl, pyranyl; quinazolinyl; isoquinolinyl; indolizinyl;isobenzofuranylnaphthyridinyl; quinoxalinyl; cinnolinyl; phthalazinyl;benzothiazolyl; benzoxazolyl; benzotriazolyl; indazolyl; indolyl;(1H-pyrrol-1-yl)-; (1H-pyrrol-2-yl)-; (1H-pyrrol-3-yl)-;(1H-pyrazol-1-yl)-; (1H-pyrazol-3-yl)-; (3H-pyrazol-3-yl)-;(1H-pyrazol-4-yl)-; (3-isoxazolyl)-; (5-isoxazolyl)-; (2-furanyl)-;(3-furanyl)-; (2-thienyl)-; (3-thienyl)-; (1H-imidazol-2-yl)-;(1H-imidazol-4-yl)-; (1H-imidazol-5-yl)-; (2-oxazol-2-yl)-;(oxazol-4-yl)-; (oxazol-5-yl)-; (thiazol-2-yl)-; (thiazol-4-yl)-;(thiazol-5-yl)-; (isothiazol-3-yl)-; (isothiazol-5-yl)-;(1H-1,2,3-triazol-1-yl)-; (1H-1,2,4-triazol-3-yl)-;(4H-1,2,4-triazol-4-yl)-; (1H-1,2,4-triazol-1-yl)-;(1,2,3-oxadiazol-2-yl)-; (1,2,4-oxadiazol-3-yl)-;(1,2,4-oxadiazol-4-yl)-; (1,2,4-oxadiazol-5-yl)-;(1,2,3-thiadiazol-2-yl)-; (1,2,4-thiadiazol-3-yl)-;(1,2,4-thiadiazol-4-yl)-; (1,3,4-thiadiazol-5-yl)-; (1H-tetrazol-1-yl)-;(1H-tetrazol-5-yl)-; (2H-tetrazol-5-yl)-; (2-pyridyl)-; (3-pyridyl)-;(4-pyridyl)-; (2-pyrimidinyl)-; (4-pyrimidinyl)-; (5-pyrimidinyl)-;(2-pyrazinyl)-; (3-pyridazinyl)-; (4-pyridazinyl)-;(1,3,5-triazin-2-yl)-; (1,2,4-triazin-5-yl)-; (1,2,4-triazin-6-yl)-;(1,2,4-triazin-3-yl)-; (furazan-3-yl)-; (2-quinolinyl)-;(3-quinolinyl)-; (4-quinolinyl)-; (5-quinolinyl)-; (6-quinolinyl)-;(3-isoquinolnyl)-; (4-isoquinolnyl)-; (2-quinozolinyl)-;(2-quinoxalinyl)-; (5-quinoxalinyl)-; (pyrido[2,3-b]pyrazin-7-yl)-;(benzoxazol-5-yl)-; (benzothiazol-5-yl)-; (benzo[b]thien-2-yl)- and(benzo[1,2,5]oxadiazol-5-yl)-; indolinyl and tetrahydroquinolynyl.

In preferred compounds of formula I, Q is selected from the groupconsisting of J-0 to J-50:

wherein each group J-0 to J-50 is mono- di- or trisubstituted with Rx,wherein

each Rx is, independently selected from the group consisting ofhydrogen, halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl.

A preferred group of compounds of formula I is represented by thecompounds of formula I-1

wherein R₂, R₄, A, X and Q are as defined under formula I above; andwherein R₁ is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl; R₄is hydrogen, halogen or C₁-C₃haloalkyl; X₁ is N-methyl, oxygen orsulfur; and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of the compounds of formula I-1.

In said preferred group of compounds of formula I-1, R₂ is preferablyC₁-C₄haloalkyl, halogen, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinylor C₁-C₄haloalkylsulfonyl; X is SO₂; R₁ is preferably ethyl; X₁ ispreferably N-methyl; and R₄ is preferably hydrogen or C₁-C₂haloalkyl.

In said preferred group of compounds of formula I-1, Q is selected fromthe group consisting of J-0 to J-50 (where the arrow represents thepoint of attachment of the heterocycle to the radical Q):

wherein each group J-0 to J-50 is mono- di- or trisubstituted with Rx,wherein each Rx is, independently selected from the group consisting ofhydrogen, halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl.

Further preferred compounds of formula I are represented by thecompounds of formula I-2

wherein R₂, R₄, A, X and Q are as defined under formula I above; andwherein R₁ is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl; R₄is hydrogen, halogen or C₁-C₃haloalkyl; X₁ is N-methyl, oxygen orsulfur; and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of the compounds of formula I-2.

In said preferred group of compounds of formula I-2, R₂ is preferablyC₁-C₄haloalkyl, halogen, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinylor C₁-C₄haloalkylsulfonyl; X is SO₂; R₁ is preferably ethyl; X₁ ispreferably N-methyl; and R₄ is preferably hydrogen or C₁-C₂haloalkyl.

In said preferred group of compounds of formula I-2, Q is selected fromthe group consisting of J-0 to J-50 (where the arrow represents thepoint of attachment of the heterocycle to the radical Q):

wherein each group J-0 to J-50 is mono- di- or trisubstituted with Rx,wherein each Rx is, independently from each other, selected from thegroup consisting of hydrogen, halogen, cyano, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄alkylsulfanyl,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, —C(O)C₁-C₄alkyl,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyland —C(O)C₁-C₄haloalkyl.

In particular preferred compounds of formula I-1 are those of formulaI-1a

wherein

A is N or CH;

X is S or SO₂;

R₁ is C₁-C₄alkyl;

R₂ is C₁-C₄haloalkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl orC₁-C₄haloalkylsulfonyl;

R₄ is hydrogen or C₁-C₂haloalkyl;

Q_(a1) is selected from the group consisting of the substituents

wherein each Rx is, independently from each other, selected from thegroup consisting of hydrogen, halogen, cyano, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄alkylsulfanyl,C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, —C(O)C₁-C₄alkyl,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyland —C(O)C₁-C₄haloalkyl.

More preferred compounds of formula I-1a are those, in which each Rx is,independently from each other, selected from hydrogen, halogen,C₁-C₄alkyl and C₁-C₄haloalkyl.

An especially preferred group of compounds of formula I-1a arerepresented by the compounds of formula I-1a2

wherein

A is N or CH;

R₂ is C₁-C₂haloalkyl, C₁-C₂haloalkylsulfanyl, C₁-C₂haloalkylsulfinyl orC₁-C₂haloalkylsulfonyl;

R₄ is hydrogen or C₁-C₂haloalkyl;

and Q_(a1) is selected from the group consisting of the substituents

wherein each Rx, independently from each other, is hydrogen, halogen,C₁-C₄alkyl or C₁-C₄haloalkyl.

In said preferred compounds of formula I-1a2, Rx is, independently fromeach other, preferably halogen, hydrogen or C₁-C₄haloalkyl; R₁ ispreferably ethyl; and R₄ is preferably hydrogen.

In particular preferred compounds of formula I-1a2 are those, in whichQ_(a1) is selected from J-0z1, J-0z2, J0z3, J-1_(z), J-5_(z), J-30_(z)and J-43_(z);

wherein each Rx is, independently from each other, hydrogen, halogen orC₁-C₄haloalkyl.

More highly preferred compounds of formula I-2 are those of formula I-2a

wherein

A is N or CH;

X is S or SO₂;

R₁ is C₁-C₄alkyl;

R₂ is C₁-C₄haloalkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl orC₁-C₄haloalkylsulfonyl;

R₄ is hydrogen or C₁-C₁-C₂haloalkyl;

Q_(a1) is is preferably selected from the group consisting of thesubstituents

wherein each Rx is, independently from each other, selected fromhydrogen, halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl.

More preferred compounds of formula I-2a, are those in which each Rx is,independently from each other, selected from, hydrogen, halogen,C₁-C₄alkyl, and C₁-C₄haloalkyl;

An especially preferred group of compounds of formula I-2a isrepresented by the compounds of formula I-2a2

wherein

A is N or CH;

R₂ is C₁-C₂haloalkyl, C₁-C₂haloalkylsulfanyl, C₁-C₂haloalkylsulfinyl orC₁-C₂haloalkylsulfonyl;

R₄ is hydrogen or C₁-C₂haloalkyl;

and Q_(a1) is selected from the group of the substituents;

wherein each Rx is, independently from each other, hydrogen, halogen,C₁-C₄alkyl or C₁-C₄haloalkyl.

In said preferred compounds of formula I-2a2, each Rx is, independentlyfrom each other, preferably halogen, hydrogen, or C₁-C₄haloalkyl; R₁ ispreferably ethyl; and R₄ is preferably hydrogen.

Most highly preferred compounds of formula I-2a2 are those in whichQ_(a1) is selected from J-0z1, J-0z2, J0z3, J-1_(z), J-5_(z), J-30_(z),and J-43_(z);

wherein each Rx is, independently from each other, hydrogen, halogen orC₁-C₄haloalkyl.

In all of the preferred embodiments of the compounds of formula Imentioned above, the substituents Q and Qa₁ are preferably selected from

a) phenyl, which can be substituted by halogen or C₁-C₄haloalkyl;

b) pyrazole, which can be substituted by C₁-C₄haloalkyl;

d) cyclopropyl, which can be substituted by cyano;

e) triazole, which can be substituted by halogen;

f) C₂-C₆alkinyl, which can be substituted by phenyl, wherein said phenylcan be substituted by halogen; and

g) C₂-C₆alkenyl, which can be substituted by phenyl, wherein said phenylcan be substituted by halogen.

A particular preferred embodiment of the compounds of formula I isrepresented by the compounds of formula I-2a3

wherein

R₂ is C₁-C₄haloalkyl;

R₄ is hydrogen or C₁-C₄alkyl; and

Q is selected from

a) phenyl, which can be substituted by halogen or C₁-C₄haloalkyl;

b) pyrazole, which can be substituted by C₁-C₄haloalkyl;

d) cyclopropyl, which can be substituted by cyano;

e) triazole, which can be substituted by halogen;

f) C₂-C₆alkinyl, which can be substituted by phenyl, wherein said phenylcan be substituted by halogen; and

g) C₂-C₆alkenyl, which can be substituted by phenyl, wherein said phenylcan be substituted by halogen.

In a further embodiment of this invention, compounds of formula I arepreferred, wherein

R₁ is C₁-C₄alkyl;

R₂ is C₁-C₄haloalkyl or C₁-C₄haloalkylsulfanyl;

R₃ is hydrogen;

R₄ is hydrogen or C₁-C₄haloalkyl;

Q is phenyl, which can be mono-, di- or trisubstituted by substituentsselected from the group consisting of halogen and C₁-C₄haloalkyl; or

Q is C₂-C₆alkenyl which can be mono-substituted by phenyl, which phenylitself can be mono-substituted by C₁-C₄haloalkyl; or

Q is pyrazolyl which can be mono-substituted by C₁-C₄haloalkyl orhalogen; or

Q is pyrimidinyl or C₃-C₆cycloalkyl, said cycloalkyl can be substitutedby cyano; or

Q is triazolyl which can be substituted by halogen; or

Q is C₁-C₄alkyl which can be substituted by cyano; or

Q is C₂-C₆alkynyl which can be mono-substituted by phenyl, which phenylitself can be mono-or disubstituted by halogen;

X is S or SO₂;

X₁ is N—C₁-C₄alkyl; in particular N—CH₃;

A is CH or N; and

A₁ is CH or N.

The process according to the invention for preparing compounds offormula I is carried out in principle by methods known to those skilledin the art, and as described below:

Compounds of formula I, wherein A, A₁, R₂, R₁, R₃, R₄, X, X₁ and Q areas defined in formula I, can prepared (as shown in scheme 1) by a Suzukireaction, which involves for example, reacting compounds of formula II,wherein Xb₁ is a leaving group, for example, chlorine, bromine oriodine, or an aryl- or alkylsulfonate such as trifluoromethanesulfonatewith compounds of formula IIIa, wherein Y_(b1) can be a boron-derivedfunctional group, as for example B(OH)₂ or B(OR_(b1))₂ wherein R_(b1)can be a C₁-C₄alkyl group or the two groups OR_(b1) can form togetherwith the boron atom a five membered ring, as for example a pinacolboronic ester. The reaction can be catalyzed by a palladium basedcatalyst, for example tetrakis(triphenylphosphine)-palladium or(1,1′bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane(1:1 complex), in presence of a base, like sodium carbonate or cesiumfluoride, in a solvent or a solvent mixture, like, for example a mixtureof 1,2-dimethoxyethane and water, or of dioxane and water, preferablyunder an inert atmosphere. The reaction temperature can preferentiallyrange from room temperature to the boiling point of the reactionmixture. Such Suzuki reactions are well known to those skilled in theart and have been reviewed, for example J. Orgmet. Chem. 576, 1999,147-168.

Alternatively compounds of formula I can be prepared by a Stillereaction of compounds of formula IIIb wherein Y_(b2) is a trialkyl tinderivative, preferably tri-n-butyl tin, with compounds of formula II.Such Stille reactions are usually carried out in the presence of apalladium catalyst, for exampletetrakis(triphenylphosphine)palladium(0), or(1,1′bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane(1:1 complex), in an inert solvent such as DMF, acetonitrile, ordioxane, optionally in the presence of an additive, such as cesiumfluoride, or lithium chloride, and optionally in the presence of afurther catalyst, for example copper(I)iodide. Such Stille couplings arealso well known to those skilled in the art, and have been described infor example J. Org. Chem., 2005, 70, 8601-8604, J. Org. Chem., 2009, 74,5599-5602, and Angew. Chem. Int. Ed., 2004, 43, 1132-1136.

Compounds of formula I wherein Q is a nitrogen bearing heterocyclicsystem, and wherein A, A₁, R₂, R₁, R₃, R₄, X, X₁, and Q are as definedin formula I, can be prepared from compounds of formula II, wherein A,A₁, R₂, R₁, R₃, R₄, X, and X₁ are as defined in formula I, and Xb₁ is aleaving group such as chlorine, bromine or iodine, or an aryl- oralkylsulfonate such as trifluoromethanesulfonate by reacting theheterocycle Q (which contains a an appropriate NH functionality), in thepresence of a base, for example an alkaline metal hydride such as sodiumhydride, or an alkali metal carbonate, for example cesium or potassiumcarbonate, optionally in the presence of a copper catalyst, for examplecopper (I) iodide in an inert solvent such as N-methyl pyrollidione orDMF at temperatures between 30-150° C. This reaction is particularlyfavored for compounds of formula I wherein A is methane. Alternativelysuch compounds can be prepared from compounds of formula II by reactionof the heterocycle Q (which contains a an appropriate NH functionality),in the presence of a base, for example an alkaline metal hydride such assodium hydride, or an alkali metal carbonate, for example cesium orpotassium carbonate, in an appropriate solvent such as N-methylpyrollidione or DMF at temperatures between 30-150° C. The reaction isillustrated for the heterocycle J-30_(z) in scheme 2, which givescompounds of formula Iaa, wherein A, A₁, R₂, R₁, R₃, R₄, X and R_(x) areas previously defined.

Compounds of formula I can also be prepared (as depicted in scheme 3) bya Suzuki reaction as described above, which involves reacting compoundsof formula IV with compounds of formula V, wherein X_(b2) can be ahalogen, preferentially chlorine, bromine or iodine, or a sulfonate,like for example a trifluoromethanesulfonate and Y_(b3) can be aboron-derived functional group, as for example B(OH)₂ or B(OR_(b2))₂wherein R_(b2) can be a C₁-C₄alkyl group or the two groups OR_(b2) canform together with the boron atom a five membered ring, as for example apinacol boronic ester. In formula IV, A, A₁, X, X₁, R₁, R₂, R₃, and R₄,are as described in formula I.

The reaction can be catalyzed by a palladium based catalyst, for exampletetrakis(triphenylphosphine)-palladium, in presence of a base, likesodium carbonate, in a solvent or a solvent mixture, like, for example amixture of 1,2-dimethoxyethane and water, preferably under inertatmosphere. The reaction temperature can preferentially range roomtemperature to the boiling point of the reaction mixture.

In a similar manner, compounds of formula I can be prepared by a Stillecoupling (Scheme 3) of compounds of formula V with compounds of formulaVI, wherein A, A₁, A₂, X, X₁, R₁, R₂, R₃, and R₄, are as describedabove, and Y_(b4) is a trialkyl tin derivative, preferably tri-n-butyltin, under conditions described as in scheme 1.

Compounds of formula IIa, wherein A is nitrogen and A₁, X₁, R₁, R₂, R₃and R₄ are as described in formula I, and Xb1 is chlorine or bromine,can be prepared according to the methods shown in scheme 4:

Thus, compounds of formula IVa are oxidized by methods known to thoseskilled in the art and described in for example, in WO 2010/125985, togive compounds of formula VIIa, wherein A₁, X₁, R₁, R₂, R₃ and R₄ are asdescribed in formula I and Xb1 is chloride or bromide. Compounds offormula VIIa upon treatment with phosphorus oxychloride or phosphorusoxychloride, optionally in the presence of a base, such astriethylamine, and optionally in a solvents, for exampledichloromethane, DMF, or dioxane (see for example Syn. Comm., 31(16),2507-2511, 2001) Compounds of formula II wherein A is CH, i.e. compoundsof formula IIb, can be prepared as shown in scheme 5:

Thus, compounds of formula IVb can be halogenated to compounds offormula VIIb, wherein A₁, X₁, R₁, R₂, R₃ and R₄ are as described informula I and Xb1 is chloride or bromide, for example with bromine orchlorine in an appropriate solvent, for example glacial acetic acid, attemperatures between 0° C. and 150° C., optionally in a microwavereactor. Alternatively the reaction may be carried out in the presenceof a Lewis acid catalyst, for example iron, or Aluminum trichloride(Friedel-Craft halogenation). Similar reactions have been described Ithe literature (see for example Ger. Offen., 19840337, 2000, Med. Chem.Lett., 3(6), 450-453; 2012 and Macromolecules, 47(14), 4607-4614; 2014).Oxidation of VIIb according methods known to those skilled in the art,and described for example in WO 2010/125985, leads to compounds offormula IIb, wherein A₁, X₁, R₁, R₂, R₃ and R₄ are as described informula I and Xb1 is chloride or bromide.

Compounds of formula I can also be prepared by reaction of a compound offormula VIII,

wherein X, R₁, R₃, R₄, Q and A are as described under formula I above,with a compound of formula IX,

wherein A₁ and R₂ are as described under formula I above, and wherein R₅is hydrogen or as described under formula I above, in the presence of ade-hydrating agent, such as for example polyphosphoric acid attemperature between 150° C. to 250° C., to yield compounds of formula I,wherein the substituents are as described above and under formula I.Such processes are well known and have been described for example in WO2008/128968, WO 2012/086848, WO 2013/018928, WO 2014/142292 and WO2006/003440. The process is summarized in scheme 6 for compounds offormula Ia:

As can be seen in scheme 6, the formation of compounds of formula Iaoccurs through the intermediacy of a compound of formula X (and/or itsposition isomer Xa). Intermediates X or intermediate Xa may form as apure entity, or intermediates X and Xa may arise as a mixture ofregioisomeric acylation products. It is in many cases advantageous tothus prepare compounds of formula (Ia) through such intermediates X/Xa,which may be isolated and optionally purified. This is illustrated forcompounds of formula Ia in scheme 7:

Compounds of the formula X and/or Xa (or a mixture thereof), or a saltthereof, wherein Q is as defined above, and wherein X, R₁, R₂, R₃, R₄, Aand A1 are as described under formula I above, and wherein R₅ ishydrogen or as described under formula I above, may be prepared by

i) activation of compound of formula VIII, wherein Q is as definedabove, by methods known to those skilled in the art and described in,for example, Tetrahedron, 2005, 61 (46), 10827-10852, to form anactivated species VIIIa, wherein Q is as defined above and wherein X₀₁is halogen, preferably chlorine. For example, compounds VIIIa where X₀₁is halogen, preferably chlorine, are formed by treatment of VIII with,for example, oxalyl chloride (COCl)₂ or thionyl chloride SOCl₂ in thepresence of catalytic quantities of N,N-dimethylformamide (DMF) in inertsolvents such as methylene chloride or tetrahydrofurane at temperaturesbetween 20 to 100° C., preferably 25° C. Alternatively, treatment ofcompounds of formula VIII with, for example,1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or dicyclohexylcarbodiimide (DCC) will generate an activated species VIIIa, wherein X₀₁is

respectively, in an inert solvent, such as pyridine or tetrahydrofurane,optionally in the presence of a base, such as triethylamine, attemperatures between 25-180° C.; followed by

ii) treatment of the activated species VIIIa with a compound of formulaIX (or a salt thereof), wherein wherein A₁ and R₂ are as described underformula I above, and R₅ is hydrogen, C₁-C₄alkyl, C₂-C₆alkenyl,C₂-C₆alkynyl, C₁-C₄alkoxy-C₁-C₄alkyl or C₃-C₆cycloalkyl, optionally inthe presence of a base, such as triethylamine or pyridine, in an inertsolvents such as dichloromethane, tetrahydrofurane, dioxane or toluene,at temperatures between 0 and 80° C., to form the compounds of formula Xand/or Xa (or a mixture thereof).

Compounds of formula X and/or Xa (or a mixture thereof) may further beconverted into compounds of formula Ia, wherein Q is as defined above,and wherein A, A₁, R₁, R₂, R₃ and R₄ are as described are as describedunder formula I above, and wherein R₅ is hydrogen or as described underformula I above, by dehydration, e.g. by heating the compounds X and/orXa (or a mixture thereof) in the presence of an acid catalyst, such asfor example methane sulfonic acid, or para-toluene sulfonic acid (TsOH),in an inert solvent such as N-methyl pyrrolidine at temperatures between25-180° C., preferably 100-170° C., optionally under microwaveconditions, or by heating in acetic acid at temperatures between100-180° C. Such processes have been described previously, for example,in WO 2010/125985 and WO2015/000715. Compounds of formula VIII areobtained by hydrolysis of compounds of formula VIIIb, VIIIc and VIIId(see below), using conditions known to those skilled in the art. Analternative synthesis of compounds of formula I is illustrated in scheme8.

As shown in scheme 8 compounds of formula XII, wherein R₁, R₄ are asdescribed in formula I, and Xb3 is halogen, can be reacted with acompound of IIIa (Suzuki reaction) or IIIb, as described previously inScheme 1 to give compounds of formula VIIIb. Alternatively compounds offormula XII can be reacted with compounds of formula XIII, wherein Q isa heterocycle and the hydrogen is attached to a nitrogen atom of thatheterocycle, in the presence of a base, optionally in the presence of acopper catalyst. The chemistry is similar to that illustrated in scheme2. Compounds of formula VIIIb are then treated with ammonia in asuitable solvent, for example methanol or ethanol to give the amides offormula XI, wherein R₁, R₄ and Q are as described in formula I. Reactionof the amides of formula XI with compounds of formula IXa, wherein A₁,R₂ and X₁ are as described in formula I, leads to compounds of formulaXc. Such an amide nitrogen heteroarylation reaction, typically runsunder transition metal-catalysed C—N bond formation conditions involvinga catalytic system (such as for example [1,1′-bis(diphenylphosphino)ferrocene] dichloropalladium(II)), usually composed of a metal, such asa palladium source (for example palladium(0) precursors likePd₂(dibenzylideneacetone)₃, or palladium(II) precursors like Pd(OAc)₂)and a ligand (for example phosphine-based or N-heterocycliccarbene-based), a base, such as alkoxides (for example sodium orpotassium tert-butoxide), carbonates, phosphates or silyl amides (forexample potassium or cesium carbonate, potassium phosphate, or lithiumhexamethyl disilazane) or hydroxides (for example sodium or potassiumhydroxide), and solvents such as toluene, tetrahydrofurane, dioxane,dimethoxyethane, N,N-dimethyl formamide, N-methyl pyrrolidone anddimethylsulfoxide, as well as their aqueous solutions. These methods areknown to those skilled in the art and described, for example, in WO2014/142292. Under those above described amide cross-coupling reactionconditions, the compounds of formula Xc can be isolated, and convertedto compounds of formula Ib as described in scheme 7) but may alsospontaneously ring-close into the compounds of formula Ib, especially incases where X₁ is NR₅. Oxidation of compounds of formula Ib to compoundsof formula I can be achieved by methods those known to those skilled inthe art, for example with meta-chloro perbenzoic acid in an inertsolvent such as chloroform or methylene chloride. Alternatively thesequence of reactions can be modified so that compound of formula XI isfirst oxidised to a compound of formula XIa, and then converted tocompounds of formula I using the same reactions previously described.Compounds of formula XIIa and XIIb can be obtained by the reactionsshown in schemes 9 and 10.

In scheme 9, compounds of formula XIV, wherein R₀₀₁ is C₁-C₄alkyl, canbe oxidized and the N-oxides of formula XV converted to compounds offormula XII using methodology described in scheme 4. Similarly,compounds of formula XIVa, wherein R₀₀₁ is C₁-C₄alkyl, can behalogenated to compounds of formula XVa, and then converted to compoundsof formula XIIb using the chemistry described in scheme 5. Compounds offormula IV are known in the literature for example in WO2015/000715.Compounds of formula XIV and XIVa have been described for example in WO2014132971, WO 2014123205, WO 2014119670, WO 2014119679, WO 2014119674,WO 2014119699, WO 2014119672, and WO 2014104407. Compounds of formulaIXa are either described in the literature (see for example WO2014/142292) or commercially available.

Compounds of formula I wherein Q is C₃-C₆cycloalkyl, or C₃-C₆cycloalkylmono- or polysubstituted by substituents selected from the groupconsisting of halogen, cyano, C₁-C₄haloalkyl, and phenyl, may beprepared by methods described above (in particular, compounds of formulaI wherein Q is cyclopropyl may be prepared by a Suzuki reactioninvolving cyclopropyl-boronic acid according to descriptions made inscheme 1). For the special case of compounds of formula I wherein Q isC₃-C₆cycloalkyl substituted by cyano (e.g. compounds Iaaa) andC₁-C₄haloalkyl (e.g. compounds Iaab), the compounds can be prepared bythe methods shown in scheme 11.

As shown in scheme 11, treatment of compounds of formula II, wherein Xis S, SO or SO₂ (in particular SO₂), and wherein A1, A, X₁, R₁, R₂, R₃and R₄ are as defined above, and in which Xb₁ is a leaving group like,for example, chlorine, bromine or iodine (preferably bromine), or anaryl- or alkylsulfonate such as trifluoromethanesulfonate, withtrimethylsilyl-acetonitrile (TMSCN), in the presence of zinc(II)fluorideZnF₂, and a palladium(0)catalyst such astris(dibenzylideneacetone)dipalladium(0)-chloroform adduct (Pd₂(dba)₃),with a ligand, for example Xantphos, in an inert solvent, such asN,N-dimethylformamide DMF at temperatures between 100-180° C.,optionally under microwave heating, leads to compounds of formula Iaaa,wherein X is S, SO or SO₂ (in particular SO₂). Such chemistry has beendescribed in the literature, e.g. in Org. Lett. 16(24), 6314-6317, 2014.Compounds of formula Iaaa can be treated with compounds of formula XVII,wherein Qx is a direct bond or is (CH₂)_(n) and n is 1, 2 or 3, and inwhich Xb₁₀ is a leaving group such as a halogen (preferably chlorine,bromine or iodine), in the presence of a base such as sodium hydride,potassium carbonate K₂CO₃, or cesium carbonate Cs₂CO₃, in an inertsolvent such as N,N-dimethylformamide DMF, acetone, or acetonitrile, attemperatures between 0-120° C., to give compounds of formula Iaab,wherein X is S, SO or SO₂ (in particular SO₂), and wherein A₁, A, X₁,R₁, R_(2,) R₃ and R₄ are as defined above and in which Qx is a directbond or is (CH₂)_(n) and n is 1, 2 or 3.

Alternatively, compounds of formula Iaa can be prepared directly fromcompounds of formula II by treatment with compounds of formula XVI,wherein Qx is is as described in XVII, in presence of a catalyst such asPd₂(dba)₃, with a ligand, such as BINAP, a strong base such as lithiumhexamethyldisilazane LiHMDS, in an inert solvent such as tetrahydrofuranTHF, at temperatures between 30-80° C. Such chemistry has been describedin, for example, J. Am. Chem. Soc. 127(45), 15824-15832, 2005.

Compounds of the formula Iaab may further be utilized for thepreparation of compounds of formula Iaac and Iaad (scheme 15). Indeed,compounds of formula Iaab, wherein X is S, SO or SO₂, and wherein A₁, A,X₁, R₁, R_(2,) R₃ and R₄ are as defined above and in which Qx is adirect bond or is (CH₂)_(n) and n is 1, 2 or 3, may be hydrolyzed, underconditions known to a person skilled in the art (aqueous basic or acidicconditions; for example, lithium or sodium hydroxide in an alcoholicsolvent such as methanol, at temperatures between 20° C. to refluxingconditions), to compounds of formula Iaac, wherein X is S, SO or SO₂,and wherein A₁, A, X₁, R₁, R_(2,) R₃ and R₄ are as defined above and inwhich Qx is a direct bond or is (CH₂)_(n) and n is 1, 2 or 3. Treatmentof compounds of formula Iaac with reagents such as sulfur tetrafluorideSF₄ or Fluolead (4-tert-butyl-2,6-dimethyl phenylsulfur trifluoride),optionally in the presence of hydrogen fluoride HF, at temperaturesbetween 20-100° C., leads to compounds of formula Iaad, wherein X is S,SO or SO₂, and wherein A₁, A, X₁, R₁, R_(2,) R₃ and R₄ are as definedabove and in which Qx is a direct bond or is (CH₂)_(n) and n is 1, 2 or3.

Compounds of the formula Iaab may also be utilized for the preparationof compounds of formula Iaae (scheme 12).

As shown in scheme 12, compounds of formula Iaab, wherein X is S, SO orSO₂, and wherein A₁, A, X₁, R₁, R_(2,) R₃ and R₄ are as defined aboveand in which Qx is a direct bond or is (CH₂)_(n) and n is 1, 2 or 3, maybe hydrolyzed, under conditions known to a person skilled in the art(aqueous basic or acidic conditions; for example, lithium or sodiumhydroxide in an alcoholic solvent such as methanol, at temperaturesbetween 20° C. to refluxing conditions; or aqueous sulphuric acid,optionally in presence of a co-solvent, at temperatures between 20° C.to refluxing conditions), to compounds of formula Iaae, wherein X is S,SO or SO₂, and wherein A₁, A, X₁, R₁, R_(2,) R₃ and R₄ are as definedabove and in which Qx is a direct bond or is (CH₂)_(n) and n is 1, 2 or3.

Alternatively compounds of formula Iaab can be prepared as shown inschemes 13 and 14. As shown in scheme 13, the chemistry used isidentical to that described in scheme 11, it is just that the substratesfor the reactions are different. Thus, reaction of the previouslydescribed compounds XIIa or XIIb, wherein X is S or SO₂ (in particularSO₂), and wherein A, R₁, R₃ and R₄ are as defined above, and in whichXb₃ is a halogen like, for example, chlorine, bromine or iodine(preferably chlorine), or an aryl- or alkylsulfonate such astrifluoromethanesulfonate, and in which R₀₀₀₁ is C₁-C₄alkyl, withtrimethylsilyl-acetonitrile TMSCN as described in scheme 11, leads tocompounds of formula XVIII, wherein X is S or SO₂ (in particular SO₂),and wherein A, R₁, R₃ and R₄ are as defined above, and in which R₀₀₁ isC₁-C₄alkyl. These are converted into compounds of formula VIIId, whereinX is S or SO₂ (in particular SO₂), and wherein Qx, wherein A, R₁, R₃ andR₄ are as defined above, and in which R₀₀₁ is C₁-C₄alkyl, by reactingwith compounds of formula XVII as described in scheme 11. Compounds offormula VIIId are readily hydrolysed by methods known to those skilledin the art to give compounds of formula VIIIe, wherein X is S or SO₂ (inparticular SO₂), and wherein Qx A, R₁, R₃ and R₄ are as defined above.

The chemistry shown in scheme 14 has previously been described in detail(see, for example, scheme 7). This chemistry involves forming anactivated species VIIIf, wherein X is S, or SO₂ (in particular SO₂), andwherein Qx, A, R₁, R₃ and R₄ are as defined above, and in which LG₁typically is chlorine, followed by amide coupling with a compound offormula IXb, wherein X₁, A₁ and R₂ are as previously defined, to givethe compounds of formula Xd. Those compounds of formula Xd can in turnbe converted to compounds of formula Iaab by a formal dehydration step,previously described in scheme 7. All substituent definitions in scheme14 are as described previously.

The reactants can be reacted in the presence of a base. Examples ofsuitable bases are alkali metal or alkaline earth metal hydroxides,alkali metal or alkaline earth metal hydrides, alkali metal or alkalineearth metal amides, alkali metal or alkaline earth metal alkoxides,alkali metal or alkaline earth metal acetates, alkali metal or alkalineearth metal carbonates, alkali metal or alkaline earth metaldialkylamides or alkali metal or alkaline earth metal alkylsilylamides,alkylamines, alkylenediamines, free or N-alkylated saturated orunsaturated cycloalkylamines, basic heterocycles, ammonium hydroxidesand carbocyclic amines. Examples which may be mentioned are sodiumhydroxide, sodium hydride, sodium amide, sodium methoxide, sodiumacetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide,potassium carbonate, potassium hydride, lithium diisopropylamide,potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine,diisopropylethylamine, triethylenediamine, cyclohexylamine,N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine,4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine,benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU).

The reactants can be reacted with each other as such, i.e. withoutadding a solvent or diluent. In most cases, however, it is advantageousto add an inert solvent or diluent or a mixture of these. If thereaction is carried out in the presence of a base, bases which areemployed in excess, such as triethylamine, pyridine, N-methylmorpholineor N,N-diethylaniline, may also act as solvents or diluents.

The reaction is advantageously carried out in a temperature range fromapproximately −80° C. to approximately +140° C., preferably fromapproximately −30° C. to approximately +100° C., in many cases in therange between ambient temperature and approximately +80° C.

A compound of formula I can be converted in a manner known per se intoanother compound of formula I by replacing one or more substituents ofthe starting compound of formula I in the customary manner by (an) othersubstituent(s) according to the invention.

Depending on the choice of the reaction conditions and startingmaterials which are suitable in each case, it is possible, for example,in one reaction step only to replace one substituent by anothersubstituent according to the invention, or a plurality of substituentscan be replaced by other substituents according to the invention in thesame reaction step.

Salts of compounds of formula I can be prepared in a manner known perse. Thus, for example, acid addition salts of compounds of formula I areobtained by treatment with a suitable acid or a suitable ion exchangerreagent and salts with bases are obtained by treatment with a suitablebase or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in the customary mannerinto the free compounds I, acid addition salts, for example, bytreatment with a suitable basic compound or with a suitable ionexchanger reagent and salts with bases, for example, by treatment with asuitable acid or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in a manner known perse into other salts of compounds of formula I, acid addition salts, forexample, into other acid addition salts, for example by treatment of asalt of inorganic acid such as hydrochloride with a suitable metal saltsuch as a sodium, barium or silver salt, of an acid, for example withsilver acetate, in a suitable solvent in which an inorganic salt whichforms, for example silver chloride, is insoluble and thus precipitatesfrom the reaction mixture.

Depending on the procedure or the reaction conditions, the compounds offormula I, which have salt-forming properties, can be obtained in freeform or in the form of salts.

The compounds of formula I and, where appropriate, the tautomersthereof, in each case in free form or in salt form, can be present inthe form of one of the isomers which are possible or as a mixture ofthese, for example in the form of pure isomers, such as antipodes and/ordiastereomers, or as isomer mixtures, such as enantiomer mixtures, forexample racemates, diastereomer mixtures or racemate mixtures, dependingon the number, absolute and relative configuration of asymmetric carbonatoms which occur in the molecule and/or depending on the configurationof non-aromatic double bonds which occur in the molecule; the inventionrelates to the pure isomers and also to all isomer mixtures which arepossible and is to be understood in each case in this sense hereinaboveand herein below, even when stereochemical details are not mentionedspecifically in each case.

Diastereomer mixtures or racemate mixtures of compounds of formula I, infree form or in salt form, which can be obtained depending on whichstarting materials and procedures have been chosen can be separated in aknown manner into the pure diastereomers or racemates on the basis ofthe physicochemical differences of the components, for example byfractional crystallization, distillation and/or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in asimilar manner can be resolved into the optical antipodes by knownmethods, for example by recrystallization from an optically activesolvent, by chromatography on chiral adsorbents, for examplehigh-performance liquid chromatography (HPLC) on acetyl cellulose, withthe aid of suitable microorganisms, by cleavage with specific,immobilized enzymes, via the formation of inclusion compounds, forexample using chiral crown ethers, where only one enantiomer iscomplexed, or by conversion into diastereomeric salts, for example byreacting a basic end-product racemate with an optically active acid,such as a carboxylic acid, for example camphor, tartaric or malic acid,or sulfonic acid, for example camphorsulfonic acid, and separating thediastereomer mixture which can be obtained in this manner, for exampleby fractional crystallization based on their differing solubilities, togive the diastereomers, from which the desired enantiomer can be setfree by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to theinvention not only by separating suitable isomer mixtures, but also bygenerally known methods of diastereoselective or enantioselectivesynthesis, for example by carrying out the process according to theinvention with starting materials of a suitable stereochemistry.

N-oxides can be prepared by reacting a compound of the formula I with asuitable oxidizing agent, for example the H₂O₂/urea adduct in thepresence of an acid anhydride, e.g. trifluoroacetic anhydride. Suchoxidations are known from the literature, for example from J. Med.Chem., 32 (12), 2561-73, 1989 or WO 00/15615.

It is advantageous to isolate or synthesize in each case thebiologically more effective isomer, for example enantiomer ordiastereomer, or isomer mixture, for example enantiomer mixture ordiastereomer mixture, if the individual components have a differentbiological activity.

The compounds of formula I and, where appropriate, the tautomersthereof, in each case in free form or in salt form, can, if appropriate,also be obtained in the form of hydrates and/or include other solvents,for example those which may have been used for the crystallization ofcompounds which are present in solid form.

The compounds according to the following Tables 1 to 6 below can beprepared according to the methods described above. The examples whichfollow are intended to illustrate the invention and show preferredcompounds of formula I.

TABLE X This table discloses the 33 substituent designations X.001 toX.033 for the formulae (Iaa), (Iab), (Iac). (Iad), (Iae) and (Iaf) whichare disclosed after Table X. Comp. No Q X.001

X.002

X.003

X.004

X.005

X.006

X.007

X.008

X.009

X.010

X.011

X-012

X-013

X.014

X.015

X.016

X.017

X.018

X-019

X-020

X-021

X-022

X-023

X-024

X-025

X-026

X-027

X-028

X-029

X-030

X-031

X-032

X-033

Table 1:

This table discloses the 33 compounds 1.001 to 1.033 of the formula(Iaa):

wherein n is 0, and R₂ is CF₃, R₁ is ethyl, R₄ is hydrogen and Q is asdefined in lines X.001-X.033 in table X. For example, compound 1.004 hasthe following structure:

Table 2:

This table discloses the 33 compounds 2.001 to 2.033 of the formula(Iaa) wherein n is 2, and R₂ is CF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 3:

This table discloses the 33 compounds 3.001 to 3.033 of the formula(Iaa) wherein n is 0, and R₂ is CF₂CF₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 4:

This table discloses the 33 compounds 4.001 to 4.033 of the formula(Iaa) wherein n is 2, and R₂ is CF₂CF₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 5:

This table discloses the 33 compounds 5.001 to 5.033 of the formula(Iaa) wherein n is 0, and R₂ is CF(CF₃)₂, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 6:

This table discloses the 33 compounds 6.001 to 6.033 of the formula(Iaa) wherein n is 2, and R₂ is CF(CF₃)₂, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 7:

This table discloses the 33 compounds 7.001 to 7.033 of the formula(Iaa) wherein n is 0, and R₂ is OCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 8:

This table discloses the 33 compounds 8.001 to 8.033 of the formula(Iaa) wherein n is 2, and R₂ is OCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 9:

This table discloses the 33 compounds 9.001 to 9.033 of the formula(Iaa) wherein n is 0, and R₂ is SCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 10:

This table discloses the 33 compounds 10.001 to 10.033 of the formula(Iaa) wherein n is 2, and R₂ is SCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 11:

This table discloses the 33 compounds 11.001 to 11.033 of the formula(Iaa) wherein n is 0, and R₂ is SOCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033in table X.

Table 12:

This table discloses the 33 compounds 12.001 to 12.033of the formula(Iaa) wherein n is 2, and R₂ is SOCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 13:

This table discloses the 33 compounds 13.001 to 13.033 of the formula(Iaa) wherein n is 0, and R₂ is SO₂CF₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 14:

This table discloses the 33 compounds 14.001 to 14.033 of the formula(Iaa) wherein n is 2, and R₂ is SO₂CF₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 15:

This table discloses the 33 compounds 15.001 to 15.027 of the formula(Iaa) wherein n is 0, and R₂ is Br, R₁ is ethyl, R₄ is hydrogen and Q isas defined in lines X.001-X.033 in table X.

Table 16:

This table discloses the 33 compounds 16.001 to 16.033 of the formula(Iaa) wherein n is 2, and R₂ is Br, R₁ is ethyl, R₄ is hydrogen and Q isas defined in lines X.001-X.033 in table X.

Table 17:

This table discloses the 33 compounds 17.001 to 17.033 of the formula(Iaa) wherein n is 0, and R₂ is CF₂CH₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 18:

This table discloses the 33 compounds 18.001 to 18.033 of the formula(Iaa) wherein n is 2, and R₂ is CF₂CH₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 19:

This table discloses the 33 compounds 19.001 to 19.033 of the formula(Iaa) wherein n is 0, and R₂ is OCF₂CHFCF₃, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 20:

This table discloses the 33 compounds 20.001 to 20.033 of the formula(Iaa) wherein n is 2, and R₂ is OCH₂CHFCF₃, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 21:

This table discloses the 33 compounds 21.001 to 21.033 of the formula(Iaa) wherein n is 0, and R₂ is OCH₂CHF₂, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 22:

This table discloses the 33 compounds 22.001 to 22.033 of the formula(Iaa) wherein n is 2, and R₂ is OCH₂CHF₂, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 23:

This table discloses the 33 compounds 23.001 to 23.033 of the formula(Iaa) wherein n is 0, and R₂ is C(CF₃)₂OCH₃, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 24:

This table discloses the 33 compounds 24.001 to 24.033 of the formula(Iaa) wherein n is 2, and R₂ is C(CF₃)₂OCH₃, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 25:

This table discloses the 33 compounds 25.001 to 25.033 of the formula(Iaa):

wherein n is 0, and R₂ is CF₃, R₁ is ethyl, R₄ is CF₃ and Q is asdefined in lines X.001-X.033 in table X.

Table 26:

This table discloses the 33 compounds 26.001 to 26.024 of the formula(Iaa) wherein n is 2, and R₂ is CF₃, R₁ is ethyl, R₄ is CF₃ and Q is asdefined in lines X.001-X.033 in table X.

Table 27:

This table discloses the 33 compounds 27.001 to 27.033 of the formula(Iaa) wherein n is 0, and R₂ is CF₂CF₃, R₁ is ethyl, R₄ is CF₃ and Q isas defined in lines X.001-X.033 in table X.

Table 28:

This table discloses the 28 compounds 28.001 to 28.033 of the formula(Iaa) wherein n is 2, and R₂ is CF₂CF₃, R₁ is ethyl, R₄ is CF₃ and Q isas defined in lines X.001-X.033 in table X.

Table 29:

This table discloses the 27 compounds 29.001 to 29.033 of the formula(Iaa) wherein n is 0, and R₂ is CF(CF₃)₂, R₁ is ethyl, R₄ is CF₃ and Qis as defined in lines X.001-X.033 in table X.

Table 30:

This table discloses the 33 compounds 30.001 to 30.033 of the formula(Iaa) wherein n is 2, and R₂ is CF(CF₃)₂, R₁ is ethyl, R₄ is CF₃ and Qis as defined in lines X.001-X.033 in table X.

Table 31:

This table discloses the 33 compounds 31.001 to 31.033 of the formula(Iaa) wherein n is 0, and R₂ is OCF₃, R₁ is ethyl, R₄ is CF₃ and Q is asdefined in lines X.001-X.033 in table X.

Table 32:

This table discloses the 33 compounds 32.001 to 32.033 of the formula(Iaa) wherein n is 2, and R₂ is OCF₃, R₁ is ethyl, R₄ is CF₃ and Q is asdefined in lines X.001-X.033 in table X.

Table 33:

This table discloses the 33 compounds 33.001 to 33.033 of the formula(Iaa) wherein n is 0, and R₂ is SCF₃, R₁ is ethyl, R₄ is CF₃ and Q is asdefined in lines X.001-X.033 in table X.

Table 34:

This table discloses the 33 compounds 34.001 to 34.033 of the formula(Iaa) wherein n is 2, and R₂ is SCF₃, R₁ is ethyl, R₄ is CF₃ and Q is asdefined in lines X.001-X.033 in table X.

Table 35:

This table discloses the 33 compounds 35.001 to 35.033 of the formula(Iaa) wherein n is 0, and R₂ is SOCF₃, R₁ is ethyl, R₄ is CF₃ and Q isas defined in lines X.001-X.033 in table X.

Table 36:

This table discloses the 33 compounds 36.001 to 36.033 of the formula(Iaa) wherein n is 2, and R₂ is SOCF₃, R₁ is ethyl, R₄ is CF₃ and Q isas defined in lines X.001-X.033 in table X.

Table 37:

This table discloses the 33 compounds 37.001 to 37.033 of the formula(Iaa) wherein n is 0, and R₂ is SO₂CF₃, R₁ is ethyl, R₄ is CF₃ and Q isas defined in lines X.001-X.033 in table X.

Table 38:

This table discloses the 33 compounds 38.001 to 38.033 of the formula(Iaa) wherein n is 2, and R₂ is SO₂CF₃, R₁ is ethyl, R₄ is CF₃ and Q isas defined in lines X.001-X.033 in table X.

Table 39:

This table discloses the 33 compounds 39.001 to 39.033 of the formula(Iaa) wherein n is 0, and R₂ is Br, R₁ is ethyl, R₄ is CF₃ and Q is asdefined in lines X.001-X.033 in table X.

Table 40:

This table discloses the 33 compounds 40.001 to 40.033 of the formula(Iaa) wherein n is 2, and R₂ is Br, R₁ is ethyl, R₄ is CF₃ and Q is asdefined in lines X.001-X.033 in table X.

Table 41:

This table discloses the 33 compounds 41.001 to 41.033 of the formula(Iaa) wherein n is 0, and R₂ is CF₂CH₃, R₁ is ethyl, R₄ is CF₃ and Q isas defined in lines X.001-X.033 in table X.

Table 42:

This table discloses the 33 compounds 42.001 to 42.033 of the formula(Iaa) wherein n is 2, and R₂ is CF₂CH₃, R₁ is ethyl, R₄ is CF₃ and Q isas defined in lines X.001-X.033 in table X.

Table 43:

This table discloses the 33 compounds 43.001 to 43.033 of the formula(Iaa) wherein n is 0, and R₂ is OCF₂CHFCF₃, R₁ is ethyl, R₄ is CF₃ and Qis as defined in lines X.001-X.033 in table X.

Table 44:

This table discloses the 33 compounds 44.001 to 44.033 of the formula(Iaa) wherein n is 2, and R₂ is OCF₂CHFCF₃, R₁ is ethyl, R₄ is CF₃ and Qis as defined in lines X.001-X.033 in table X.

Table 45:

This table discloses the 33 compounds 45.001 to 45.033 of the formula(Iaa) wherein n is 0, and R₂ is OCF₂CHFCF₃, R₁ is ethyl, R₄ is CF₃ and Qis as defined in lines X.001-X.033 in table X.

Table 46:

This table discloses the 33 compounds 46.001 to 46.033 of the formula(Iaa) wherein n is 2, and R₂ is OCF₂CHFCF₃, R₁ is ethyl, R₄ is CF₃ and Qis as defined in lines X.001-X.033 in table X.

Table 47:

This table discloses the 33 compounds 47.001 to 47.033 of the formula(Iaa) wherein n is 0, and R₂ is C(CF₃)₂OCH₃, R₁ is ethyl, R₄ is CF₃ andQ is as defined in lines X.001-X.033 in table X.

Table 48:

This table discloses the 33 compounds 48.001 to 48.033 of the formula(Iaa) wherein n is 2, and R₂ is C(CF₃)₂OCH₃, R₁ is ethyl, R₄ is CF₃ andQ is as defined in lines X.001-X.033 in table X.

Table 49:

This table discloses the 33 compounds 49.001 to 49.033 of the formula(Iab):

wherein n is 0, and R₂ is CF₃, R₁ is ethyl, R₄ is hydrogen and Q is asdefined in lines X.001-X.033 in table X. For example, compound 49.017has the following structure:

Table 50:

This table discloses the 33 compounds 50.001 to 50.024 of the formula(Iab) wherein n is 2, and R₂ is CF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 51:

This table discloses the 33 compounds 51.001 to 51.033 of the formula(Iab) wherein n is 0, and R₂ is CF₂CF₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 52:

This table discloses the 33 compounds 52.001 to 52.033 of the formula(Iab) wherein n is 2, and R₂ is CF₂CF₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 53:

This table discloses the 33 compounds 53.001 to 53.033 of the formula(Iab) wherein n is 0, and R₂ is CF(CF₃)₂, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 54:

This table discloses the 33 compounds 53.001 to 53.033 of the formula(Iab) wherein n is 2, and R₂ is CF(CF₃)₂, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 55:

This table discloses the 33 compounds 55.001 to 55.033 of the formula(Iab) wherein n is 0, and R₂ is SCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 56:

This table discloses the 33 compounds 56.001 to 56.033 of the formula(Iab) wherein n is 2, and R₂ is SCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 57:

This table discloses the 33 compounds 57.001 to 57.033 of the formula(Iac):

wherein n is 0, and R₂ is CF₃, R₁ is ethyl, R₄ is hydrogen and Q is asdefined in lines X.001-X.033 in table X. For example, compound 57.021has the following structure:

Table 58:

This table discloses the 33 compounds 58.001 to 58.024 of the formula(Iac) wherein n is 2, and R₂ is CF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 59:

This table discloses the 33 compounds 59.001 to 59.033 of the formula(Iac) wherein n is 0, and R₂ is CF₂CF₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 60:

This table discloses the 33 compounds 60.001 to 60.033 of the formula(Iac) wherein n is 2, and R₂ is CF₂CF₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 61:

This table discloses the 33 compounds 61.001 to 61.033 of the formula(Iac) wherein n is 0, and R₂ is CF(CF₃)₂, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 62:

This table discloses the 33 compounds 62.001 to 62.033 of the formula(Iac) wherein n is 2, and R₂ is CF(CF₃)₂, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 63:

This table discloses the 33 compounds 63.001 to 63.033 of the formula(Iac) wherein n is 0, and R₂ is SCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 64:

This table discloses the 33 compounds 64.001 to 64.033 of the formula(Iac) wherein n is 2, and R₂ is SCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 65:

This table discloses the 33 compounds 65.001 to 65.033 of the formula(Iad):

wherein n is 0, and R₂ is CF₃, R₁ is ethyl, R₄ is hydrogen and Q is asdefined in lines X.001-X.033 in table X. For example, compound 65.016has the following structure:

Table 66:

This table discloses the 33 compounds 66.001 to 66.024 of the formula(Iad) wherein n is 2, and R₂ is CF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 67:

This table discloses the 33 compounds 67.001 to 67.033 of the formula(Iad) wherein n is 0, and R₂ is CF₂CF₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 68:

This table discloses the 33 compounds 68.001 to 68.033 of the formula(Iad) wherein n is 2, and R₂ is CF₂CF₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 69:

This table discloses the 33 compounds 69.001 to 69.033 of the formula(Iad) wherein n is 0, and R₂ is CF(CF₃)₂, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 70:

This table discloses the 33 compounds 70.001 to 70.033 of the formula(Iad) wherein n is 2, and R₂ is CF(CF₃)₂, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 71:

This table discloses the 33 compounds 71.001 to 71.033 of the formula(Iad) wherein n is 0, and R₂ is SCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 72:

This table discloses the 33 compounds 72.001 to 72.033 of the formula(Iad) wherein n is 2, and R₂ is SCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 73:

This table discloses the 33 compounds 73.001 to 73.033 of the formula(Iae):

wherein n is 0, and R₂ is CF₃, R₁ is ethyl, R₄ is hydrogen and Q is asdefined in lines X.001-X.033 in table X. For example, compound 73.024has the following structure:

Table 74:

This table discloses the 33 compounds 74.001 to 74.024 of the formula(Iae) wherein n is 2, and R₂ is CF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 75:

This table discloses the 33 compounds 75.001 to 75.033 of the formula(Iae) wherein n is 0, and R₂ is CF₂CF₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 76:

This table discloses the 33 compounds 76.001 to 76.033 of the formula(Iae) wherein n is 2, and R₂ is CF₂CF₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 77:

This table discloses the 33 compounds 77.001 to 77.033 of the formula(Iae) wherein n is 0, and R₂ is CF(CF₃)₂, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 78:

This table discloses the 33 compounds 78.001 to 78.033 of the formula(Iae) wherein n is 2, and R₂ is CF(CF₃)₂, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 79:

This table discloses the 33 compounds 79.001 to 79.033 of the formula(Iae) wherein n is 0, and R₂ is SCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 80:

This table discloses the 33 compounds 80.001 to 80.033 of the formula(Iae) wherein n is 2, and R₂ is SCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 81:

This table discloses the 33 compounds 81.001 to 81.033 of the formula(Iaf):

wherein n is 0, and R₂ is CF₃, R₁ is ethyl, R₄ is hydrogen and Q is asdefined in lines X.001-X.033 in table X. For example, compound 81.007has the following structure:

Table 82:

This table discloses the 33 compounds 82.001 to 82.024 of the formula(Iaf) wherein n is 2, and R₂ is CF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 83:

This table discloses the 33 compounds 83.001 to 83.033 of the formula(Iaf) wherein n is 0, and R₂ is CF₂CF₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 84:

This table discloses the 33 compounds 84.001 to 84.033 of the formula(Iaf) wherein n is 2, and R₂ is CF₂CF₃, R₁ is ethyl, R₄ is hydrogen andQ is as defined in lines X.001-X.033 in table X.

Table 85:

This table discloses the 33 compounds 85.001 to 85.033 of the formula(Iaf) wherein n is 0, and R₂ is CF(CF₃)₂, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 86:

This table discloses the 33 compounds 86.001 to 86.033 of the formula(Iaf) wherein n is 2, and R₂ is CF(CF₃)₂, R₁ is ethyl, R₄ is hydrogenand Q is as defined in lines X.001-X.033 in table X.

Table 87:

This table discloses the 33 compounds 87.001 to 87.033 of the formula(Iaf) wherein n is 0, and R₂ is SCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

Table 88:

This table discloses the 33 compounds 88.001 to 88.033 of the formula(Iaf) wherein n is 2, and R₂ is SCF₃, R₁ is ethyl, R₄ is hydrogen and Qis as defined in lines X.001-X.033 in table X.

The compounds of formula I according to the invention are preventivelyand/or curatively valuable active ingredients in the field of pestcontrol, even at low rates of application, which have a very favourablebiocidal spectrum and are well tolerated by warm-blooded species, fishand plants. The active ingredients according to the invention actagainst all or individual developmental stages of normally sensitive,but also resistant, animal pests, such as insects or representatives ofthe order Acarina. The insecticidal or acaricidal activity of the activeingredients according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately oronly after some time has elapsed, for example during ecdysis, orindirectly, for example in a reduced oviposition and/or hatching rate.

Examples of the abovementioned animal pests are:

from the order Acarina, for example,

Acalitus spp, Aculus spp, Acaricalus spp, Aceria spp, Acarus siro,Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobiaspp, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae,Dermatophagoides spp, Eotetranychus spp, Eriophyes spp., Hemitarsonemusspp, Hyalomma spp., Ixodes spp., Olygonychus spp, Ornithodoros spp.,Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora,Phytonemus spp, Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalusspp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp,Tarsonemus spp. and Tetranychus spp.;

from the order Anoplura, for example,

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. andPhylloxera spp.;

from the order Coleoptera, for example,

Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp.,Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis,Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp.,Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp.,Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp.,Heteronychus arator, Hypothenemus hampei, Lagria vilosa, LeptinotarsadecemLineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp,Maladera castanea, Megascelis spp, Melighetes aeneus, Melolontha spp.,Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophagaspp, Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatusaubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotrogaspp., Somaticus spp, Sphenophorus spp, Sternechus subsignatus, Tenebriospp., Tribolium spp. and Trogoderma spp.;

from the order Diptera, for example,

Aedes spp., Anopheles spp, Antherigona soccata, Bactrocea oleae, Bibiohortulanus, Bradysia spp, Calliphora erythrocephala, Ceratitis spp.,Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp,Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyzatripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyzaspp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp.,Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp.,Rhagoletis spp, Rivelia quadrifasciata, Scatella spp, Sciara spp.,Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;

from the order Hemiptera, for example,

Acanthocoris scabrator, Acrosternum spp, Adelphocoris lineolatus,Amblypelta nitida, Bathycoelia thalassina, Blissus spp, Cimex spp.,Clavigralla tomentosicollis, Creontiades spp, Distantiella theobroma,Dichelops furcatus, Dysdercus spp., Edessa spp, Euchistus spp., Eurydemapulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus,Leptocorisa spp., Lygus spp, Margarodes spp, Murgantia histrionic,Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysius simulans,Oebalus insularis, Piesma spp., Piezodorus spp, Rhodnius spp.,Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp.,Thyanta spp, Triatoma spp., Vatiga illudens;

Acyrthosium pisum, Adalges spp, Agalliana ensigera, Agonoscenatargionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis,Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula,Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotusspp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp,Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariellaaegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalusdictyospermi, Cicadella spp, Cofana spectra, Cryptomyzus spp, Cicadulinaspp, Coccus hesperidum, Dalbulus maidis, Dialeurodes spp, Diaphorinacitri, Diuraphis noxia, Dysaphis spp, Empoasca spp., Eriosoma larigerum,Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphispseudobrassicae, Hyalopterus spp, Hyperomyzus pallidus, Idioscopusclypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni,Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp.,Mahanarva spp, Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus,Myzus spp., Neotoxoptera sp, Nephotettix spp., Nilaparvata spp.,Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter,Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigusspp., Peregrinus maidis, Perkinsiella spp, Phorodon humuli, Phylloxeraspp, Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp.,Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica,Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphumspp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp.,Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina,Toxoptera spp, Trialeurodes spp, Tridiscus sporoboli, Trionymus spp,Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidiascutellaris;

from the order Hymenoptera, for example,

Acromyrmex, Arge spp, Atta spp., Cephus spp., Diprion spp., Diprionidae,Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis,Neodiprion spp., Pogonomyrmex spp, Slenopsis invicta, Solenopsis spp.and Vespa spp.;

from the order Isoptera, for example,

Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermesspp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsisgeminate

from the order Lepidoptera, for example,

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabamaargillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,Argyresthia spp, Argyrotaenia spp., Autographa spp., Bucculatrixthurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis,Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysiaambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp.,Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp,Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis,Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea,Earias spp., Eldana saccharina, Ephestia spp., Epinotia spp, Estigmeneacrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella,Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedyanubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp,Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus,Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostegebifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestrabrassicae, Manduca sexta, Mythimna spp, Noctua spp, Operophtera spp.,Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp.,Panolis flammea, Papaipema nebris, Pectinophora gossypiela,Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaeaoperculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp.,Pseudoplusia spp, Rachiplusia nu, Richia albicosta, Scirpophaga spp.,Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate,Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tutaabsoluta, and Yponomeuta spp.;

from the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.;

from the order Orthoptera, for example,

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae,Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscusspp, and Schistocerca spp.;

from the order Psocoptera, for example,

Liposcelis spp.;

from the order Siphonaptera, for example,

Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;

from the order Thysanoptera, for example,

Calliothrips phaseoli, Frankliniella spp., Heliothrips spp,Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii,Sericothrips variabilis, Taeniothrips spp., Thrips spp;

from the order Thysanura, for example, Lepisma saccharina.

The active ingredients according to the invention can be used forcontrolling, i. e. containing or destroying, pests of the abovementionedtype which occur in particular on plants, especially on useful plantsand ornamentals in agriculture, in horticulture and in forests, or onorgans, such as fruits, flowers, foliage, stalks, tubers or roots, ofsuch plants, and in some cases even plant organs which are formed at alater point in time remain protected against these pests.

Suitable target crops are, in particular, cereals, such as wheat,barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodderbeet; fruit, for example pomaceous fruit, stone fruit or soft fruit,such as apples, pears, plums, peaches, almonds, cherries or berries, forexample strawberries, raspberries or blackberries; leguminous crops,such as beans, lentils, peas or soya; oil crops, such as oilseed rape,mustard, poppies, olives, sunflowers, coconut, castor, cocoa or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants,such as cotton, flax, hemp or jute; citrus fruit, such as oranges,lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce,asparagus, cabbages, carrots, onions, tomatoes, potatoes or bellpeppers; Lauraceae, such as avocado, Cinnamonium or camphor; and alsotobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines,hops, the plantain family and latex plants.

The compositions and/or methods of the present invention may be alsoused on any ornamental and/or vegetable crops, including flowers,shrubs, broad-leaved trees and evergreens.

For example the invention may be used on any of the following ornamentalspecies: Ageratum spp., Alonsoa spp., Anemone spp., Anisodonteacapsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp.(e.g. B. elatior, B. semperflorens, B. tubéreux), Bougainvillea spp.,Brachycome spp., Brassica spp. (ornamental), Calceolaria spp., Capsicumannuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemumspp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea,Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis,Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp.,Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp.,Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp.,Hypoestes phyllostachya, Impatiens spp. (I. walleriana), Iresines spp.,Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus,Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesiaspp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp.,Bellis spp., Pelargonium spp. (P. peltatum, P. zonale), Viola spp.(pansy), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp.,Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp.,Ranunculus spp., Rhododendron spp., Rosa spp. (rose), Rudbeckia spp.,Saintpaulia spp., Salvia spp., Scaevola aemola, Schizanthuswisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp.,Nicotinia spp., Verbena spp., Zinnia spp. and other bedding plants.

For example the invention may be used on any of the following vegetablespecies: Allium spp. (A. sativum, A. cepa, A. oschaninii, A. porrum, A.ascalonicum, A. fistulosum), Anthriscus cerefolium, Apium graveolus,Asparagus officinalis, Beta vulgarus, Brassica spp. (B. oleracea, B.pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichoriumendivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus,Cucumis spp. (C. sativus, C. melo), Cucurbita spp. (C. pepo, C. maxima),Cyanara spp. (C. scolymus, C. cardunculus), Daucus carota, Foeniculumvulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L.esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum,Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisumsativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salviaspp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea,Valerianella spp. (V. locusta, V. eriocarpa) and Vicia faba.

Preferred ornamental species include African violet, Begonia, Dahlia,Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster,Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum,Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia,Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper,tomato and cucumber.

The active ingredients according to the invention are especiallysuitable for controlling Aphis craccivora, Diabrotica balteata,Heliothis virescens, Myzus persicae, Plutella xylostella and Spodopteralittoralis in cotton, vegetable, maize, rice and soya crops. The activeingredients according to the invention are further especially suitablefor controlling Mamestra (preferably in vegetables), Cydia pomonella(preferably in apples), Empoasca (preferably in vegetables, vineyards),Leptinotarsa (preferably in potatoes) and Chilo supressalis (preferablyin rice).

In a further aspect, the invention may also relate to a method ofcontrolling damage to plant and parts thereof by plant parasiticnematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasiticnematodes), especially plant parasitic nematodes such as root knotnematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogynejavanica, Meloidogyne arenaria and other Meloidogyne species;cyst-forming nematodes, Globodera rostochiensis and other Globoderaspecies; Heterodera avenae, Heterodera glycines, Heterodera schachtii,Heterodera trifolii, and other Heterodera species; Seed gall nematodes,Anguina species; Stem and foliar nematodes, Aphelenchoides species;Sting nematodes, Belonolaimus longicaudatus and other Belonolaimusspecies; Pine nematodes, Bursaphelenchus xylophilus and otherBursaphelenchus species; Ring nematodes, Criconema species, Criconemellaspecies, Criconemoides species, Mesocriconema species; Stem and bulbnematodes, Ditylenchus destructor, Ditylenchus dipsaci and otherDitylenchus species; Awl nematodes, Dolichodorus species; Spiralnematodes, Heliocotylenchus multicinctus and other Helicotylenchusspecies; Sheath and sheathoid nematodes, Hemicycliophora species andHemicriconemoides species; Hirshmanniella species; Lance nematodes,Hoploaimus species; false rootknot nematodes, Nacobbus species; Needlenematodes, Longidorus elongatus and other Longidorus species; Pinnematodes, Pratylenchus species; Lesion nematodes, Pratylenchusneglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchusgoodeyi and other Pratylenchus species; Burrowing nematodes, Radopholussimilis and other Radopholus species; Reniform nematodes, Rotylenchusrobustus, Rotylenchus reniformis and other Rotylenchus species;Scutellonema species; Stubby root nematodes, Trichodorus primitivus andother Trichodorus species, Paratrichodorus species; Stunt nematodes,Tylenchorhynchus claytoni, Tylenchorhynchus dubius and otherTylenchorhynchus species; Citrus nematodes, Tylenchulus species; Daggernematodes, Xiphinema species; and other plant parasitic nematodespecies, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp.,Melinius spp., Punctodera spp., and Quinisulcius spp.

The compounds of the invention may also have activity against themolluscs. Examples of which include, for example, Ampullariidae; Arion(A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae(Bradybaena fruticum); Cepaea (C. hortensis, C. nemoralis); ochlodina;Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum);Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H.itala, H. obvia); Helicidae Helicigona arbustorum); Helicodiscus; Helix(H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L.maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M.sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising one or more selectively acting toxins,such as are known, for example, from toxin-producing bacteria,especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins, for example insecticidal proteins fromBacillus cereus or Bacillus popilliae; or insecticidal proteins fromBacillus thuringiensis, such as δ-endotoxins, e.g. Cry1Ab, Cry1Ac,Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetativeinsecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A; orinsecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood byδ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A,Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for exampleVip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncatedtoxins and modified toxins.

Hybrid toxins are produced recombinantly by a new combination ofdifferent domains of those proteins (see, for example, WO 02/15701).Truncated toxins, for example a truncated Cry1Ab, are known. In the caseof modified toxins, one or more amino acids of the naturally occurringtoxin are replaced. In such amino acid replacements, preferablynon-naturally present protease recognition sequences are inserted intothe toxin, such as, for example, in the case of Cry3A055, acathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO03/018810).

Examples of such toxins or transgenic plants capable of synthesisingsuch toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278,WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. CryI-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGardRootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGardPlus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin);Starlink® (maize variety that expresses a Cry9C toxin); Herculex I®(maize variety that expresses a Cry1Fa2 toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses aCry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac anda Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and aCry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin);NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated Cry1Ab toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a Cry1Ab toxin. Bt176 maize also transgenicallyexpresses the enzyme PAT to achieve tolerance to the herbicideglufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCry3A toxin. This toxin is Cry3A055 modified by insertion of acathepsin-G-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a Cry3Bb1 toxin and has resistance to certain Coleopterainsects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. Geneticallymodified maize for the expression of the protein Cry1F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.

7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a Cry1Ab toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS(Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS,Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising antipathogenic substances having aselective action, such as, for example, the so-called“pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225).Examples of such antipathogenic substances and transgenic plants capableof synthesising such antipathogenic substances are known, for example,from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. The methods ofproducing such transgenic plants are generally known to the personskilled in the art and are described, for example, in the publicationsmentioned above.

Crops may also be modified for enhanced resistance to fungal (forexample Fusarium, Anthracnose, or Phytophthora), bacterial (for examplePseudomonas) or viral (for example potato leafroll virus, tomato spottedwilt virus, cucumber mosaic virus) pathogens.

Crops also include those that have enhanced resistance to nematodes,such as the soybean cyst nematode.

Crops that are tolerance to abiotic stress include those that haveenhanced tolerance to drought, high salt, high temperature, chill,frost, or light radiation, for example through expression of NF-YB orother proteins known in the art.

Antipathogenic substances which can be expressed by such transgenicplants include, for example, ion channel blockers, such as blockers forsodium and calcium channels, for example the viral KP1, KP4 or KP6toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases;the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392225); antipathogenic substances produced by microorganisms, for examplepeptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818)or protein or polypeptide factors involved in plant pathogen defence(so-called “plant disease resistance genes”, as described in WO03/000906).

Further areas of use of the compositions according to the invention arethe protection of stored goods and store rooms and the protection of rawmaterials, such as wood, textiles, floor coverings or buildings, andalso in the hygiene sector, especially the protection of humans,domestic animals and productive livestock against pests of the mentionedtype.

The present invention also provides a method for controlling pests (suchas mosquitoes and other disease vectors; see alsohttp://www.who.int/malaria/vector_control/irs/en/). In one embodiment,the method for controlling pests comprises applying the compositions ofthe invention to the target pests, to their locus or to a surface orsubstrate by brushing, rolling, spraying, spreading or dipping. By wayof example, an IRS (indoor residual spraying) application of a surfacesuch as a wall, ceiling or floor surface is contemplated by the methodof the invention. In another embodiment, it is contemplated to applysuch compositions to a substrate such as non-woven or a fabric materialin the form of (or which can be used in the manufacture of) netting,clothing, bedding, curtains and tents.

In one embodiment, the method for controlling such pests comprisesapplying a pesticidally effective amount of the compositions of theinvention to the target pests, to their locus, or to a surface orsubstrate so as to provide effective residual pesticidal activity on thesurface or substrate. Such application may be made by brushing, rolling,spraying, spreading or dipping the pesticidal composition of theinvention. By way of example, an IRS application of a surface such as awall, ceiling or floor surface is contemplated by the method of theinvention so as to provide effective residual pesticidal activity on thesurface. In another embodiment, it is contemplated to apply suchcompositions for residual control of pests on a substrate such as afabric material in the form of (or which can be used in the manufactureof) netting, clothing, bedding, curtains and tents.

Substrates including non-woven, fabrics or netting to be treated may bemade of natural fibres such as cotton, raffia, jute, flax, sisal,hessian, or wool, or synthetic fibres such as polyamide, polyester,polypropylene, polyacrylonitrile or the like. The polyesters areparticularly suitable. The methods of textile treatment are known, e.g.WO 2008/151984, WO 2003/034823, U.S. Pat. No. 5,631,072, WO 2005/64072,WO2006/128870, EP 1724392, WO2005113886 or WO 2007/090739.

Further areas of use of the compositions according to the invention arethe field of tree injection/trunk treatment for all ornamental trees aswell all sort of fruit and nut trees.

In the field of tree injection/trunk treatment, the compounds accordingto the present invention are especially suitable against wood-boringinsects from the order Lepidoptera as mentioned above and from the orderColeoptera, especially against woodborers listed in the following tablesA and B:

TABLE A Examples of exotic woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus planipennis AshCerambycidae Anoplura glabripennis Hardwoods Scolytidae Xylosandruscrassiusculus Hardwoods X. mutilatus Hardwoods Tomicus piniperdaConifers

TABLE B Examples of native woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus anxius Birch Agriluspolitus Willow, Maple Agrilus sayi Bayberry, Sweetfern Agrilusvittaticolllis Apple, Pear, Cranberry, Serviceberry, HawthornChrysobothris femorata Apple, Apricot, Beech, Boxelder, Cherry,Chestnut, Currant, Elm, Hawthorn, Hackberry, Hickory, Horsechestnut,Linden, Maple, Mountain-ash, Oak, Pecan, Pear, Peach, Persimmon, Plum,Poplar, Quince, Redbud, Serviceberry, Sycamore, Walnut, Willow Texaniacampestris Basswood, Beech, Maple, Oak, Sycamore, Willow, Yellow-poplarCerambycidae Goes pulverulentus Beech, Elm, Nuttall, Willow, Black oak,Cherrybark oak, Water oak, Sycamore Goes tigrinus Oak Neoclytusacuminatus Ash, Hickory, Oak, Walnut, Birch, Beech, Maple, Easternhophornbeam, Dogwood, Persimmon, Redbud, Holly, Hackberry, Black locust,Honeylocust, Yellow-poplar, Chestnut, Osage-orange, Sassafras, Lilac,Mountain- mahogany, Pear, Cherry, Plum, Peach, Apple, Elm, Basswood,Sweetgum Neoptychodes trilineatus Fig, Alder, Mulberry, Willow, Netleafhackberry Oberea ocellata Sumac, Apple, Peach, Plum, Pear, Currant,Blackberry Oberea tripunctata Dogwood, Viburnum, Elm, Sourwood,Blueberry, Rhododendron, Azalea, Laurel, Poplar, Willow, MulberryOncideres cingulata Hickory, Pecan, Persimmon, Elm, Sourwood, Basswood,Honeylocust, Dogwood, Eucalyptus, Oak, Hackberry, Maple, Fruit treesSaperda calcarata Poplar Strophiona nitens Chestnut, Oak, Hickory,Walnut, Beech, Maple Scolytidae Corthylus columbianus Maple, Oak,Yellow-poplar, Beech, Boxelder, Sycamore, Birch, Basswood, Chestnut, ElmDendroctonus frontalis Pine Dryocoetes betulae Birch, Sweetgum, Wildcherry, Beech, Pear Monarthrum fasciatum Oak, Maple, Birch, Chestnut,Sweetgum, Blackgum, Poplar, Hickory, Mimosa, Apple, Peach, PinePhloeotribus liminaris Peach, Cherry, Plum, Black cherry, Elm, Mulberry,Mountain-ash Pseudopityophthorus Oak, American beech, Black cherry,pruinosus Chickasaw plum, Chestnut, Maple, Hickory, Hornbeam,Hophornbeam Sesiidae Paranthrene simulans Oak, American chestnut Sanninauroceriformis Persimmon Synanthedon exitiosa Peach, Plum, Nectarine,Cherry, Apricot, Almond, Black cherry Synanthedon pictipes Peach, Plum,Cherry, Beach, Black Cherry Synanthedon rubrofascia Tupelo Synanthedonscitula Dogwood, Pecan, Hickory, Oak, Chestnut, Beech, Birch, Blackcherry, Elm, Mountain- ash, Viburnum, Willow, Apple, Loquat, Ninebark,Bayberry Vitacea polistiformis Grape

The present invention may be also used to control any insect pests thatmay be present in turfgrass, including for example beetles,caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites,mole crickets, scales, mealybugs ticks, spittlebugs, southern chinchbugs and white grubs. The present invention may be used to controlinsect pests at various stages of their life cycle, including eggs,larvae, nymphs and adults.

In particular, the present invention may be used to control insect peststhat feed on the roots of turfgrass including white grubs (such asCyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp.(e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green Junebeetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica),Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Blackturfgrass ataenius, A. spretulus), Maladera spp. (e.g. Asiatic gardenbeetle, M. castanea) and Tomarus spp.), ground pearls (Margarodes spp.),mole crickets (tawny, southern, and short-winged; Scapteriscus spp.,Garyllotalpa africana) and leatherjackets (European crane fly, Tipulaspp.).

The present invention may also be used to control insect pests ofturfgrass that are thatch dwelling, including armyworms (such as fallarmyworm Spodoptera frugiperda, and common armyworm Pseudaletiaunipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatusverstitus and S. parvulus), and sod webworms (such as Crambus spp. andthe tropical sod webworm, Herpetogramma phaeopteralis).

The present invention may also be used to control insect pests ofturfgrass that live above the ground and feed on the turfgrass leaves,including chinch bugs (such as southern chinch bugs, Blissus insularis),Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug(Antonina graminis), two-lined spittlebug (Propsapia bicincta),leafhoppers, cutworms (Noctuidae family), and greenbugs.

The present invention may also be used to control other pests ofturfgrass such as red imported fire ants (Solenopsis invicta) thatcreate ant mounds in turf.

In the hygiene sector, the compositions according to the invention areactive against ectoparasites such as hard ticks, soft ticks, mangemites, harvest mites, flies (biting and licking), parasitic fly larvae,lice, hair lice, bird lice and fleas.

Examples of such parasites are:

Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculusspp. and Phtirus spp., Solenopotes spp.

Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

Of the order Diptera and the suborders Nematocerina and Brachycerina,for example Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

Of the order Siphonapterida, for example Pulex spp., Ctenocephalidesspp., Xenopsylla spp., Ceratophyllus spp.

Of the order Heteropterida, for example Cimex spp., Triatoma spp.,Rhodnius spp., Panstrongylus spp.

Of the order Blattarida, for example Blatta orientalis, Periplanetaamericana, Blattelagermanica and Supella spp.

Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata,for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp.,Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp.,Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp.,Pneumonyssus spp., Sternostoma spp. and Varroa spp.

Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), forexample Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobiaspp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorusspp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp.,Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp.,Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. andLaminosioptes spp.

The compositions according to the invention are also suitable forprotecting against insect infestation in the case of materials such aswood, textiles, plastics, adhesives, glues, paints, paper and card,leather, floor coverings and buildings.

The compositions according to the invention can be used, for example,against the following pests: beetles such as Hylotrupes bajulus,Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum,Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobiumcarpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctuslinearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis,Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychuscapucins, Heterobostrychus brunneus, Sinoxylon spec. and Dinoderusminutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas,Urocerus gigas taignus and Urocerus augur, and termites such asKalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis andCoptotermes formosanus, and bristletails such as Lepisma saccharina.

The compounds according to the invention can be used as pesticidalagents in unmodified form, but they are generally formulated intocompositions in various ways using formulation adjuvants, such ascarriers, solvents and surface-active substances. The formulations canbe in various physical forms, e.g. in the form of dusting powders, gels,wettable powders, water-dispersible granules, water-dispersible tablets,effervescent pellets, emulsifiable concentrates, microemulsifiableconcentrates, oil-in-water emulsions, oil-flowables, aqueousdispersions, oily dispersions, suspo-emulsions, capsule suspensions,emulsifiable granules, soluble liquids, water-soluble concentrates (withwater or a water-miscible organic solvent as carrier), impregnatedpolymer films or in other forms known e.g. from the Manual onDevelopment and Use of FAO and WHO Specifications for Pesticides, UnitedNations, First Edition, Second Revision (2010). Such formulations caneither be used directly or diluted prior to use. The dilutions can bemade, for example, with water, liquid fertilisers, micronutrients,biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingredientwith the formulation adjuvants in order to obtain compositions in theform of finely divided solids, granules, solutions, dispersions oremulsions. The active ingredients can also be formulated with otheradjuvants, such as finely divided solids, mineral oils, oils ofvegetable or animal origin, modified oils of vegetable or animal origin,organic solvents, water, surface-active substances or combinationsthereof.

The active ingredients can also be contained in very fine microcapsules.Microcapsules contain the active ingredients in a porous carrier. Thisenables the active ingredients to be released into the environment incontrolled amounts (e.g. slow-release). Microcapsules usually have adiameter of from 0.1 to 500 microns. They contain active ingredients inan amount of about from 25 to 95% by weight of the capsule weight. Theactive ingredients can be in the form of a monolithic solid, in the formof fine particles in solid or liquid dispersion or in the form of asuitable solution. The encapsulating membranes can comprise, forexample, natural or synthetic rubbers, cellulose, styrene/butadienecopolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides,polyureas, polyurethane or chemically modified polymers and starchxanthates or other polymers that are known to the person skilled in theart. Alternatively, very fine microcapsules can be formed in which theactive ingredient is contained in the form of finely divided particlesin a solid matrix of base substance, but the microcapsules are notthemselves encapsulated.

The formulation adjuvants that are suitable for the preparation of thecompositions according to the invention are known per se. As liquidcarriers there may be used: water, toluene, xylene, petroleum ether,vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acidanhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone,butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkylesters of acetic acid, diacetone alcohol, 1,2-dichloropropane,diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycolabietate, diethylene glycol butyl ether, diethylene glycol ethyl ether,diethylene glycol methyl ether, N,N-dimethylformamide, dimethylsulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methylether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone,ethyl acetate, 2-ethylhexanol, ethylene carbonate,1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyllactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycolmethyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glyceroldiacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamylacetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene,isopropyl myristate, lactic acid, laurylamine, mesityl oxide,methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyllaurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene,n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleicacid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid,propyl lactate, propylene carbonate, propylene glycol, propylene glycolmethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol,xylenesulfonic acid, paraffin, mineral oil, trichloroethylene,perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propyleneglycol methyl ether, diethylene glycol methyl ether, methanol, ethanol,isopropanol, and alcohols of higher molecular weight, such as amylalcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol,propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like.

Suitable solid carriers are, for example, talc, titanium dioxide,pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone,calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks,wheat flour, soybean flour, pumice, wood flour, ground walnut shells,lignin and similar substances.

A large number of surface-active substances can advantageously be usedin both solid and liquid formulations, especially in those formulationswhich can be diluted with a carrier prior to use. Surface-activesubstances may be anionic, cationic, non-ionic or polymeric and they canbe used as emulsifiers, wetting agents or suspending agents or for otherpurposes. Typical surface-active substances include, for example, saltsof alkyl sulfates, such as diethanolammonium lauryl sulfate; salts ofalkylarylsulfonates, such as calcium dodecylbenzenesulfonate;alkylphenol/alkylene oxide addition products, such as nonylphenolethoxylate; alcohol/alkylene oxide addition products, such astridecylalcohol ethoxylate; soaps, such as sodium stearate; salts ofalkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate;dialkyl esters of sulfosuccinate salts, such as sodiumdi(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitololeate; quaternary amines, such as lauryltrimethylammonium chloride,polyethylene glycol esters of fatty acids, such as polyethylene glycolstearate; block copolymers of ethylene oxide and propylene oxide; andsalts of mono- and di-alkylphosphate esters; and also further substancesdescribed e.g. in McCutcheon's Detergents and Emulsifiers Annual, MCPublishing Corp., Ridgewood N.J. (1981).

Further adjuvants that can be used in pesticidal formulations includecrystallisation inhibitors, viscosity modifiers, suspending agents,dyes, anti-oxidants, foaming agents, light absorbers, mixingauxiliaries, antifoams, complexing agents, neutralising or pH-modifyingsubstances and buffers, corrosion inhibitors, fragrances, wettingagents, take-up enhancers, micronutrients, plasticisers, glidants,lubricants, dispersants, thickeners, antifreezes, microbicides, andliquid and solid fertilisers.

The compositions according to the invention can include an additivecomprising an oil of vegetable or animal origin, a mineral oil, alkylesters of such oils or mixtures of such oils and oil derivatives. Theamount of oil additive in the composition according to the invention isgenerally from 0.01 to 10%, based on the mixture to be applied. Forexample, the oil additive can be added to a spray tank in the desiredconcentration after a spray mixture has been prepared. Preferred oiladditives comprise mineral oils or an oil of vegetable origin, forexample rapeseed oil, olive oil or sunflower oil, emulsified vegetableoil, alkyl esters of oils of vegetable origin, for example the methylderivatives, or an oil of animal origin, such as fish oil or beeftallow. Preferred oil additives comprise alkyl esters of C₈-C₂₂ fattyacids, especially the methyl derivatives of C₁₂-C₁₈ fatty acids, forexample the methyl esters of lauric acid, palmitic acid and oleic acid(methyl laurate, methyl palmitate and methyl oleate, respectively). Manyoil derivatives are known from the Compendium of Herbicide Adjuvants,10^(th) Edition, Southern Illinois University, 2010.

The inventive compositions generally comprise from 0.1 to 99% by weight,especially from 0.1 to 95% by weight, of compounds of the presentinvention and from 1 to 99.9% by weight of a formulation adjuvant whichpreferably includes from 0 to 25% by weight of a surface-activesubstance. Whereas commercial products may preferably be formulated asconcentrates, the end user will normally employ dilute formulations.

The rates of application vary within wide limits and depend on thenature of the soil, the method of application, the crop plant, the pestto be controlled, the prevailing climatic conditions, and other factorsgoverned by the method of application, the time of application and thetarget crop. As a general guideline compounds may be applied at a rateof from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.

Preferred formulations can have the following compositions (weight %):

Emulsifiable Concentrates:

active ingredient: 1 to 95%, preferably 60 to 90%

surface-active agent: 1 to 30%, preferably 5 to 20%

liquid carrier: 1 to 80%, preferably 1 to 35%

Dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 5%

solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension Concentrates:

active ingredient: 5 to 75%, preferably 10 to 50%

water: 94 to 24%, preferably 88 to 30%

surface-active agent: 1 to 40%, preferably 2 to 30%

Wettable Powders:

active ingredient: 0.5 to 90%, preferably 1 to 80%

surface-active agent: 0.5 to 20%, preferably 1 to 15%

solid carrier: 5 to 95%, preferably 15 to 90%

Granules:

active ingredient: 0.1 to 30%, preferably 0.1 to 15%

solid carrier: 99.5 to 70%, preferably 97 to 85%

The following Examples further illustrate, but do not limit, theinvention.

Wettable powders a) b) c) active ingredients 25% 50% 75% sodiumlignosulfonate  5%  5% — sodium lauryl sulfate  3% —  5% sodiumdiisobutylnaphthalenesulfonate —  6% 10% phenol polyethylene glycolether —  2% — (7-8 mol of ethylene oxide) highly dispersed silicic acid 5% 10% 10% Kaolin 62% 27% —

The combination is thoroughly mixed with the adjuvants and the mixtureis thoroughly ground in a suitable mill, affording wettable powders thatcan be diluted with water to give suspensions of the desiredconcentration.

Powders for dry seed treatment a) b) c) active ingredients 25% 50% 75%light mineral oil  5%  5%  5% highly dispersed silicic acid  5%  5% —Kaolin 65% 40% — Talcum — 20   

The combination is thoroughly mixed with the adjuvants and the mixtureis thoroughly ground in a suitable mill, affording powders that can beused directly for seed treatment.

Emulsifiable concentrate active ingredients 10% octylphenol polyethyleneglycol ether  3% (4-5 mol of ethylene oxide) calciumdodecylbenzenesulfonate  3% castor oil polyglycol ether  4% (35 mol ofethylene oxide) Cyclohexanone 30% xylene mixture 50%

Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Dusts a) b) c) Active ingredients  5%  6%  4% Talcum 95% — — Kaolin —94% — mineral filler — — 96%

Ready-for-use dusts are obtained by mixing the combination with thecarrier and grinding the mixture in a suitable mill. Such powders canalso be used for dry dressings for seed.

Extruder granules Active ingredients 15% sodium lignosulfonate  2%carboxymethylcellulose  1% Kaolin 82%

The combination is mixed and ground with the adjuvants, and the mixtureis moistened with water. The mixture is extruded and then dried in astream of air.

Coated granules Active ingredients  8% polyethylene glycol (mol. wt.200)  3% Kaolin 89%

The finely ground combination is uniformly applied, in a mixer, to thekaolin moistened with polyethylene glycol. Non-dusty coated granules areobtained in this manner.

Suspension concentrate active ingredients 40% propylene glycol 10%nonylphenol polyethylene glycol ether  6% (15 mol of ethylene oxide)Sodium lignosulfonate 10% carboxymethylcellulose  1% silicone oil (inthe form of a 75%  1% emulsion in water) Water 32%

The finely ground combination is intimately mixed with the adjuvants,giving a suspension concentrate from which suspensions of any desireddilution can be obtained by dilution with water. Using such dilutions,living plants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.

Flowable concentrate for seed treatment active ingredients   40%propylene glycol   5% copolymer butanol PO/EO   2% Tristyrenephenolewith 10-20 moles EO   2% 1,2-benzisothiazolin-3-one  0.5% (in the formof a 20% solution in water) monoazo-pigment calcium salt   5% Siliconeoil (in the form of a 75%  0.2% emulsion in water) Water 45.3%

The finely ground combination is intimately mixed with the adjuvants,giving a suspension concentrate from which suspensions of any desireddilution can be obtained by dilution with water. Using such dilutions,living plants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.

Slow Release Capsule Suspension

28 parts of the combination are mixed with 2 parts of an aromaticsolvent and 7 parts of toluenediisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). Thismixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol,0.05 parts of a defoamer and 51.6 parts of water until the desiredparticle size is achieved. To this emulsion a mixture of 2.8 parts1,6-diaminohexane in 5.3 parts of water is added. The mixture isagitated until the polymerization reaction is completed. The obtainedcapsule suspension is stabilized by adding 0.25 parts of a thickener and3 parts of a dispersing agent. The capsule suspension formulationcontains 28% of the active ingredients. The medium capsule diameter is8-15 microns. The resulting formulation is applied to seeds as anaqueous suspension in an apparatus suitable for that purpose.

Formulation types include an emulsion concentrate (EC), a suspensionconcentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), awater dispersible granule (WG), an emulsifiable granule (EG), anemulsion, water in oil (EO), an emulsion, oil in water (EW), amicro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable(OF), an oil miscible liquid (OL), a soluble concentrate (SL), anultra-low volume suspension (SU), an ultra-low volume liquid (UL), atechnical concentrate (TK), a dispersible concentrate (DC), a wettablepowder (WP), a soluble granule (SG) or any technically feasibleformulation in combination with agriculturally acceptable adjuvants.

PREPARATORY EXAMPLES

“Mpt.” means melting point in ° C. Free radicals represent methylgroups. ¹H NMR measurements were recorded on a Brucker 400 MHzspectrometer, chemical shifts are given in ppm relevant to a TMSstandard. Spectra measured in deuterated solvents as indicated.

LCMS Methods:

Method 1:

Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII orZQ Single quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive or negative ions, Capillary: 3.00 kV, Conerange: 30-60 V, Extractor: 2.00 V, Source Temperature: 150° C.,Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation GasFlow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC fromWaters: Binary pump, heated column compartment and diode-array detector.Solvent degasser, binary pump, heated column compartment and diode-arraydetector. Column: Waters UPLC HSS T3, 1.8 mm, 30×2.1 mm, Temp: 60° C.,DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 1.2min; Flow (mL/min) 0.85

Example H12-[3-ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Compound P3, table P)

Step A: tert-butyl N-[4-amino-6-(trifluoromethyl)-3-pyridyl]carbamate

To a solution of 6-(trifluoromethyl)pyridine-3,4-diamine (3.14 g, 17.73mmol, prepared as described in U.S. Pat. No. 7,767,687) intetrahydrofurane (50 ml) was added tert-butoxycarbonyl tert-butylcarbonate (4.64 g, 21.27 mmol) and the mixture was stirred at 50° C.After 8 hours, a further 1.1 g (5.0 mmol) of tert-butoxycarbonyltert-butyl carbonate was added, and stirring at 50° C. continued for afurther 4 hours. The reaction mixture was then concentrated in vacuo,and the brown residue was suspended in dichloromethane, filtered anddried in vacuo to give the title compound as white crystals. LCMS(method A): retention time: 0.79 min; 278 (M+H).

Step B: tert-butylN-[4-amino-6-(trifluoromethyl)-3-pyridyl]-N-methyl-carbamate

To a stirred suspension of sodium hydride (0.648 g, 14.85 mmol) in 30 mlN,N-dimethylformamide, tert-butylN-[4-amino-6-(trifluoromethyl)-3-pyridyl]carbamate (3.92 g, 14.14 mmol)dissolved in 20 ml N,N-dimethylformamide was added dropwise over aperiod of 20 min at 20-25° C. After 15 min stirring at ambienttemperature, iodomethane (2.21 g, 15.55 mmol) was added. After 30 min atambient temperature the mixture was poured onto 200 ml water, extractedtwice with ethyl acetate, and the combined organic fractions washedsuccessively with water and brine, dried over Na₂SO₄ and concentrated invacuo. The crude product was recrystallized from ethyl acetate/heptaneto give the title compound (3.18 g) as white crystals. LCMS (method A):retention time: 0.85 min; 292 (M+H).

Step C: N3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine

To a clear, colorless solution of tert-butylN-[4-amino-6-(trifluoromethyl)-3-pyridyl]-N-methyl-carbamate (3.53 g,12.119 mmol) in dioxane, hydrogen chloride (18 mL of a 2M solution inwater, 36.36 mmol) was added and the mixture was heated to reflux. Aftergas evolution had ceased, the reaction mixture was cooled to roomtemperature, and treated with solid sodium hydrogen carbonate (3.1 g,36.9 mmol). The slurry was diluted with water and extracted twice withethyl acetate. The combined organic layers were washed successively withwater and brine, dried over Na₂SO₄ and concentrated in vacuo to give2.25 g of the title compound as colorless crystals, Mpt 138-140° C. LCMS(method A): retention time 0.24 min, 192 (M+H).

Alternatively, N3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine can beobtained by the following procedure:

To a solution of 6-(trifluoromethyl)pyridine-3,4-diamine (2.0 g, 12.2mmol) and potassium carbonate (3.2 g, 23.1 mmol) in acetonitrile (10 mL)was added iodomethane (0.8 mL). The reaction mixture was stirred at 30°C. for 18 hours. Potassium carbonate was filtered off, the filtrate wasdried in vacuo and purified with chromatography column on silica geleluting with (petroleum:ethyl acetate=4:3) to afford the title compoundas a light yellow solid (0.32 g). ¹H NMR (400 MHz, DMSO-d₆): δ (ppm)7.57 (s, 1H), 6.83 (s, 1H), 5.82 (s, 2 H), 5.23 (d, J=4.8 Hz, 1H), 2.80(d, J=4.8 Hz, 3H). ¹⁹F NMR (300 MHz, DMSO-d6): δ (ppm) −60.12 (s, 3 F).

Step D:N-[4-amino-6-(trifluoromethyl)-3-pyridyl]-3-ethylsulfonyl-N-methyl-pyridine-2-carboxamideand3-ethylsulfonyl-N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamide

To a solution of N3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine(16.70 g, 87.37 mmol) in THF (167.0 mL) was added Et₃N (22.32 g, 218.4mmol). The reaction mixture cooled to 0° C. and3-ethylsulfonylpyridine-2-carbonyl chloride (18.37 g, 78.63 mmol,prepared as described in WO 2013 018928) dissolved in dichloromethane(170 mL) was added dropwise at 0-10° C. to the mixture over 1 hour.After 1.5 hours LC/MS detected desired product at Rt=0.74. The ice-bathwas removed and the reaction mixture was allowed to warm up to ambienttemperature and stirred for 12 hours. The reaction mixture was thendiluted with saturated NH₄Cl, the organic phase separated, and theaqueous phase back extracted with dichloromethane. The combined organicphases were washed with water, brine, dried over Na₂SO₄, filtered andconcentrated in vacuo to give the crude product. The crude product wasdissolved in dichloromethane and adsorbed on teflon bulk sorbents, andpurified over a silica gel cartridge (Rf200) eluting withcyclohexane/ethyl acetate. This gave the crude title product as amixture of amide region isomers that was used in the next step withoutfurther purification.

LCMS (method 1); Rt=0.73 min, [M+H] 389 and 0.8 min [M+H] 389.

Step E:2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine

A yellow solution of the crude product mixture from step D (26.72 g,68.80 mmol) in acetic 270 mL, was stirred at 120° C. over night. Aftercooling, the mixture was diluted with toluene and concentrated in vacuo.The crude product was dissolved in dichloromethane and adsorbed onteflon bulk sorbents, and purified over a silica gel cartridge (TORENT)eluting with heptane:EtOAc to give the title product as beige solid.

LCMS (method 1): retention time 0.78 minutes, (M+H)=371. ¹H NMR (400MHz, CHLOROFORM-d) δ ppm: 1.36 (t, J=7.3 Hz, 3 H); 3.77 (q, J=7.3 Hz, 2H); 3.90 (s, 3 H); 7.77 (dd, J=8.1, 4.8 Hz, 1 H); 8.12 (s, 1 H); 8.55(dd, J=8.1, 1.8 Hz, 1 H); 9.00 (s, 1 H); 9.02 (dd, J=4.8, 1.8 Hz, 1 H).

Step F:2-(3-ethylsulfonyl-1-oxido-pyridin-1-ium-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(A)

Method A:

To a solution of2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(18.70 g, 50.49 mmol) in dichloromethane (187.0 mL) was addedmeta-chloroperbenzoic acid (13.69 g, 55.53 mmol). The yellow solutionwas stirred at ambient temperature for 18 hours. After this time, thereaction mixture was cooled to ambient temperature, and diluted withaqueous sodium thiosulfate solution. The reaction mixture was extractedwith dichloromethane, the combined organic fractions washed with Na₂CO₃,dried over MgSO₄, and concentrated in vacuo. The crude product wasdissolved in dichloromethane and adsorbed on teflon bulk sorbents, andpurified over a silica gel cartridge (TORENT) eluting with heptane/ethylacetate and then dichloromethane:methanol. This gave the title productas the first eluting product.

LCMS (method 1): retention time 0.72 min, (M+H)=387. ¹H NMR (400 MHz,CHLOROFORM-d) δ ppm; 1.35 (t, J=7.5 Hz, 3 H); 3.39-3.52 (m, 1 H);3.66-3.82 (m, 1 H); 3.87 (s, 3 H); 7.71 (dd, J=8.1, 6.6 Hz, 1 H); 8.00(dd, J=8.1, 0.7 Hz, 1 H); 8.13 (d, J=0.7 Hz, 1 H); 8.55 (dd, J=6.6, 0.7Hz, 1 H) 9.03 (s, 1 H).

As second eluting product was

2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-5-oxido-6-(trifluoromethyl)imidazo[4,5-c]pyridin-5-ium(B)

LCMS (method 1): retention time 0.64 min, (M+H)=387. ¹H NMR (400 MHz,CHLOROFORM-d) δ ppm: 1.37 (t, J=7.5 Hz, 3 H); 3.76 (q, J=7.5 Hz, 2 H);3.77 (s, 3H); 7.77 (dd, J=8.1, 4.8 Hz, 1 H); 8.09 (s, 1 H); 8.55 (dd,J=8.1, 1.5 Hz, 1 H); 8.71 (s, 1 H); 9.01 (dd, J=4.8, 1.5 Hz, 1 H).

As third eluting product was isolated

2-(3-ethylsulfonyl-1-oxido-pyridin-1-ium-2-yl)-3-methyl-5-oxido-6-(trifluoromethyl)imidazo[4,5-c]pyridin-5-ium(C)

LCMS (method 1): retention time 0.55 min, (M+H)=403. ¹H NMR (400 MHz,CHLOROFORM-d) δ ppm: 1.36 (t, J=7.3 Hz, 3 H); 3.33-3.54 (m, 1 H);3.60-3.80 (m, 1 H); 7.72 (dd, J=8.1, 6.6 Hz, 1 H); 7.99 (dd, J=8.1, 0.7Hz, 1 H); 8.10 (s, 1 H); 8.54 (dd, J=6.6, 0.7 Hz, 1 H); 8.68 (s, 1 H).

The ratio of the products was (A):(B):(C) 9:15:1.

Method B:

To a solution of2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(1.00 g, 2.70 mmol) and urea hydrogen peroxide (0.288 g, 1.10 eq, 2.97mmol) in dichloromethane (10.0 mL) was slowly added trifluoroacetic acidanhydride (1.15 g, 0.759 mL, 5.40 mmol) at 0° C. After 30 min theice-bath was removed and the reaction mixture was allowed to warm toambient temperature.

LC/MS after 3 hours detected desired product at Rt=0.72, product B atRt=0.64, and product D at Rt=0.55 It was stirred over the weekend atambient temperature. Work-up and purification according to method A gavethe same three products (A):(B):(C) in a ratio of 9:3:1.

Step G:2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine

2-(3-ethylsulfonyl-1-oxido-pyridin-1-ium-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(1.38 g, 1.00 eq, 3.57 mmol) and phosphoryl chloride (29.61 g, 18 mL,53.5 eq, 191.2 mmol) were mixed in micro wave vial and heated at 130° C.for 6 hours in the microwave. LC/MS after this time showed reactioncompletion. The reaction mixture was concentrated in vacuo and purifiedover silica gel cartridge (Rf200), eluting with cyclohexane:ethylacetate to give the title compound as a white solid:

LCMS (method 1): retention time 0.95 minutes, (M+H)=405/407. ¹H NMR (400MHz, CHLOROFORM-d) δ ppm: 1.41 (t, J=7.5 Hz, 3 H); 3.64 (q, J=7.5 Hz, 2H); 4.11 (s, 3 H); 7.89 (d, J=8.4 Hz, 1 H); 8.49 (d, J=8.4 Hz, 1 H);9.65 (s, 1 H).

Step H:2-[3-ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Compound P3, table P)

A solution of 3-(trifluoromethyl)-1H-pyrazole (0.034 g, 0.25 mmol) inDMF (2.0 mL, 26 mmol) was cooled to 0° C. and treated with sodiumhydride (60% in oil, 0.013 g, 0.32 mmol). The reaction was stirred 20min at 0° C. and then treated with2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(0.10 g, 0.25 mmol) and the reaction allowed to warm and stirred atambient temperature. LCMS showed reaction completion after 30 min. Thereaction was diluted with tert-butyl dimethyl ether, and then quenchedwith sat. NaHCO₃ sol. The organic layer was separated, washed 2× withwater and brine, dried over Na₂SO₄, filtered and concentrated in vacuo.The crude product was dissolved in dichloromethane, adsorbed onto teflonbulk sorbents, and then purified over a silica gel cartridge (Rf200),eluting with cyclohexane/ethyl acetate, to give the title compound as awhite solid. Mpt 261-263° C.

LCMS (method 1): retention time 1.07 min, (M+H)=505. ¹H NMR (400 MHz,CHLOROFORM-d) δ ppm: 1.38 (t, J=7.5 Hz, 3 H); 3.73 (q, J=7.5 Hz, 2 H);3.93 (s, 3 H); 6.80 (d, J=2.6 Hz, 1 H); 8.15 (d, J=0.7 Hz, 1 H); 8.45(d, J=8.8 Hz, 1 H); 8.59 (dd, J=2.6, 0.92 Hz, 1 H) 8.68 (d, J=8.8 Hz, 1H) 9.04 (s, 1 H).

Example H22-[6-(4-chlorophenyl)-3-ethylsulfonyl-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Compound P1, table P)

In a supelco vial,2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Step G, example P1, 0.04 g, 0.1 mmol) dissolved in 1,4-dioxane (1 mL)was treated with (4-chlorophenyl)boronic acid (0.02 g, 0.1 mmol) andanhydrous K₂CO₃ (0.04 g, 0.3 mmol) and the mixture purged with argon for10 min. Then, palladium-tris-triphenylphosphine (0.01 g, 0.01 mmol) wasadded and the solution heated at 100° C. LCMS analysis after 4 hoursshowed reaction completion. The reaction mixture was diluted with waterand ethyl acetate, the organic layer was separated, washed with brine,dried over Na₂SO₄, filtered and evaporated and concentrated in vacuo.The crude product was dissolved in dichloromethane, adsorbed onto teflonbulk sorbents, and then purified over a silica gel cartridge (Rf200),eluting with cyclohexane/ethyl acetate, to give the title compound as ayellow solid. Mpt 255-256° C.

LCMS (method 1): retention time 1.11 min, (M+H)=481/483. ¹H NMR (400MHz, CHLOROFORM-d) δ ppm: 1.39 (t, J=7.5 Hz, 3 H); 3.79 (q, J=7.5 Hz, 2H); 3.95 (s, 3 H); 7.51 (d, J=8.8 Hz, 2 H); 8.06 (d, J=8.8 Hz, 2 H);8.11 (d, J=8.4 Hz, 1 H;) 8.15 (s, 1 H); 8.57 (d, J=8.4 Hz, 1 H); 9.02(s, 1 H).

Example H32-[3-ethylsulfonyl-6-[(E)-2-[2-(trifluoromethyl)phenyl]vinyl]-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Compound P2, Table P)

In a microwave vial,2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Step G, example P1, 0.10 g, 0.25 mmol), anhydrous K₂CO₃ (0.068 g, 0.49mmol), 2-(trifluoromethyl)styrene (0.043 g, 0.037 mL, 0.25 mmol)dissolved in acetonitrile were degassed with argon. To this mixture wasadded palladium(II)acetate (0.0051 g, 0.022 mmol) and the mixture thenheated for 45 min at 140° C. after this time, a further portion of2-(trifluoromethyl)styrene (0.074 mL) and palladium (II)acetate (0.0028g, 0.050 eq, 0.012 mmol) were added and the mixture heated in themicrowave 1 hour at 140° C. After this time, the reaction mixture wasfiltered over hyflo, and the filtrate diluted with ethyl acetate andwashed successively with 1N HCl, water and brine, dried over Na₂SO₄,filtered and concentrated in vacuo. The crude product was dissolved indichloromethane, adsorbed onto teflon bulk sorbents, and then purifiedover a silica gel cartridge (Rf200), eluting with cyclohexane/ethylacetate. Further purification by reversed phase HPLC gave the titlecompound as white foam.

LCMS (method 1): retention time 1.14 min, (M+H)=541. ¹H NMR (400 MHz,CHLOROFORM-d) δ ppm: 1.40 (t, J=7.3 Hz, 3 H); 3.86 (q, J=7.34 Hz, 2 H);4.00 (s, 3 H); 7.24 (d, J=15.7 Hz, 1 H); 7.46-7.52 (m, 1 H); 7.62 (t,J=7.5 Hz, 1 H); 7.71-7.77 (m, 2 H) 7.85 (d, J=7.75 Hz, 1 H) 8.14 (s, 1H) 8.25 (dd, J=15.7, 2.20 Hz, 1 H) 8.51 (d, J=8.4 Hz, 1 H) 9.03 (s, 1H).

Example H42-[3-ethylsulfonyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Compound P4, Table P))

Step A: Methyl 3-ethylsulfanyl-5-(trifluoromethyl)pyridine-2-carboxylate

A solution of methyl 3-chloro-5-(trifluoromethyl)pyridine-2-carboxylate(30 g, 125 mmol, CAS Registry Number [655235-65-7]) was dissolved in DMF(630 mL), Sodium ethanethiolate (12.87 g, 138 mmol) was added inportions keeping the temperature below 20° C. The reaction mixture wasallowed to stir overnight after which LCMS analysis showed reactioncompletion. The mixture was diluted with water, extracted with AcOEt (3times), and the combined organic phases washed successively withsaturated aqueous NH₄Cl and brine, dried over MgSO₄ and concentrated invacuo. The crude title compound was used for the next step withoutfurther purification.

LCMS (method 1); Rt=0.96 min, [M+H] 266. ¹H NMR (400 MHz, CHLOROFORM-d)δ ppm: 1.43 (t, J=7.5 Hz, 3 H); 3.00 (q, J=7.5 Hz, 2 H); 4.04 (s, 3 H);7.87 (d, J=1.1 Hz, 1 H); 8.66 (d, J=1.1 Hz, 1 H).

Step B: methyl 3-ethylsulfonyl-5-(trifluoromethyl)pyridine-2-carboxylate

A solution of methyl3-ethylsulfanyl-5-(trifluoromethyl)pyridine-2-carboxylate (5.94 g, 22.4mmol) in dichloromethane (200 mL) was cooled to 0° C. To this solutionwas added m-CPBA (11.0 g, 44.8 mmol) in small portions at 0°. After 2hours, the solution is allowed to warm to ambient and stirred for 3hours at ambient temperature after which time LCMS showed reactioncompletion. The reaction mixture was poured onto NaHCO₃ aq. andsaturated sodium thiosulfate aqueous solution. The mixture was thenextracted with dichloromethane (3×), washed with brine, dried over MgSO₄and concentrated in vacuo.

The crude product was purified by Combi flash chromatography elutingwith a gradient of cyclohexane+0-30% ethyl acetate. This gave the titlecompound as a white solid.

LCMS (method 1); Rt=0.76 min, [M+H] 298. ¹H NMR (400 MHz, CHLOROFORM-d)δ ppm: 1.39 (t, J=7.5 Hz, 3 H); 3.57 (q, J=7.5 Hz, 2 H); 4.08 (s, 3 H);8.61 (d, J=1.8 Hz, 1 H); 9.11 (d, J=1.8 Hz, 1 H).

Step C: Methyl3-ethylsulfonyl-1-oxido-5-(trifluoromethyl)pyridin-1-ium-2-carboxylate

A solution of methyl3-ethylsulfonyl-5-(trifluoromethyl)pyridine-2-carboxylate (7.5 g, 25mmol, prepared as described in) in dichloromethane (80 mL) was cooled to0° C. and urea hydrogen peroxide complex (5.1 g, 53 mmol) added in smallportions. To this mixture was added trifluoroacetic anhydride (11 g, 7.2mL, 50.0 mmol) keeping the reaction temperature at 0° C. The reactionmixture was allowed to warm to rt and stirred overnight. After thistime, the reaction was quenched with aqueous sodium hydrogen sulfitesolution, and stirred for 15 min. The resulting mixture was poured onto0.5 M HCl and extracted 3 times with dichloromethane. The combinedorganic extracts were washed with NaHCO₃ aqueous solution, dried overNa₂SO₄, filtered and concentrated in vacuo. The crude product waspurified by Combi flash chromatography, eluting with a gradient ofcyclohexane +0-100% ethyl acetate, to give the title compound as a whitesolid.

LCMS (method 1); Rt=0.70 min, [M+H] 314. ¹H NMR (400 MHz, CHLOROFORM-d)δ ppm: 1.39 (t, J=7.5 Hz, 3 H); 3.38 (q, J=7.5 Hz, 2 H); 4.08 (s, 3 H);7.93 (d, J=0.7 Hz, 1 H); 8.62 (d, J=0.7 Hz, 1 H).

Step D: Methyl6-chloro-3-ethylsulfonyl-5-(trifluoromethyl)pyridine-2-carboxylate

A sample of methyl3-ethylsulfonyl-1-oxido-5-(trifluoromethyl)pyridin-1-ium-2-carboxylate(1.43 g, 4.57 mmol) and phosphoryl chloride (24.3 mL) were placed in twomicrowave vials and the vials stirred at 130° C. for 6 hours in themicrowave. After this time, the contents of the vials were combined andconcentrated in vacuo. The crude product was purified over silica gelcartridge (Rf200) eluting with cyclohexane/ethyl acetate to give thetitle product as white crystals.

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 1.39 (t, J=7.5 Hz, 3 H); 3.55 (q,J=7.5 Hz, 2 H); 4.07 (s, 3 H); 8.61 (s, 1 H).

Step E: Methyl3-ethylsulfonyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxylate

A solution of methyl6-chloro-3-ethylsulfonyl-5-(trifluoromethyl)pyridine-2-carboxylate(0.285 g, 0.86 mmol) in 1,4-dioxane (7 mL) was treated with[4-(trifluoromethyl)phenyl]boronic acid (0.212 g, 1.12 mmol) andanhydrous K₂CO₃ (0.356 g, 3.00 eq, 2.58 mmol) and the mixture purgedwith argon for 10 min. To this mixture was addedtetrakis(triphenylphosphine)palladium(0) (0.0993 g, 0.100 eq, 0.0859mmol) and the solution heated at 100° C. for 3 hr after which time LCMSshowed good reaction conversion. The reaction mixture was diluted withNH₄Cl sat sol, water and ethyl acetate. The organic phase was separated,washed with brine, dried over Na₂SO₄, filtered and concentrated invacuo. The crude product was dissolved in dichloromethane and adsorbedon teflon bulk sorbents. Purification over a silica gel cartridge(Rf200), eluting with cyclohexane/ethyl acetate gave the title compoundas a white solid.

LCMS (method 1); Rt=1.09 min, [M+H] 442. ¹H NMR (400 MHz, CHLOROFORM-d)δ ppm: 1.44 (t, J=7.5 Hz, 3 H); 3.59 (q, J=7.5 Hz, 2 H); 4.06 (s, 3 H);7.70 (d, J=8.0 Hz, 2 H); 7.78 (d, J=8.0 Hz, 2 H); 8.73 (s, 1 H).

Step F:3-ethylsulfonyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxylicacid

Methyl3-ethylsulfonyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxylate(0.28 g, 0.63 mmol) was dissolved in tetrahydrofuran/H₂O 3:1 (10 mL) andtreated with lithium hydroxide hydrate (0.028 g, 0.67 mmol) at ambienttemperature. LCMS analysis after stirring for 3 hours showed reaction.The reaction mixture was concentrated in vacuo and taken up in ethylacetate and 10% aqueous HCl. The organic layer was separated and washedwith brine, dried over Na₂SO₄, filtered and concentrated in vacuo togive the title compound as beige solid that was used in the next stepwithout further purification.

LCMS (method 1); Rt=0.88 min, [M+H] 428. ¹H NMR (400 MHz, CHLOROFORM-d)δ ppm 1.42 (t, J=7.3 Hz, 3 H): 3.75 (q, J=7.3 Hz, 2 H): 4.98 (br. s., 1H); 7.70 (d, J=7.8 Hz, 2 H); 7.79 (d, J=7.8 Hz, 2 H): 8.86 (s, 1 H).

Step G:3-ethylsulfonyl-N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridyl]-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxamideandN-[4-amino-6-(trifluoromethyl)-3-pyridyl]-3-ethylsulfonyl-N-methyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxamide

A solution of3-ethylsulfonyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxylicacid (0.10 g, 0.23 mmol), EDCl (0.049 g, 0.26 mmol) andN3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine (0.049 g, 0.26 mmol,step C, example P1) in pyridine (3.0 mL) was stirred at 120° C. After 2hours LC/MS showed sufficient reaction progress for work-up. Thereaction mixture was poured onto water, and extracted with ethyl acetate(×3). The combined organic layers were washed with brine, dried overNa₂SO₄ and concentrated in vacuo. The crude product was dissolved indichloromethane and adsorbed on teflon bulk sorbents. Purification overa silica gel cartridge (Rf200), eluting with cyclohexane/ethyl acetate

Gradient gave a mixture of the title compounds as a yellow solid.

LCMS (method 1); Rt=1.10 min, [M+H] 601; Rt=1.14 min, [M+H] 601.

Step H:2-[3-ethylsulfonyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Compound P4, Table P)

A yellow solution of3-ethylsulfonyl-N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridyl]-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxamideandN-[4-amino-6-(trifluoromethyl)-3-pyridyl]-3-ethylsulfonyl-N-methyl-5-(trifluoromethyl)-6-[4-(trifluoromethyl)phenyl]pyridine-2-carboxamide:(0.055 g, 0.092 mmol) in acetic acid (1 mL) was stirred at 120° C. for18 hours. LCMS analysis after this time showed reaction completion. Thereaction mixture was cooled to ambient temperature, diluted with tolueneand concentrated in vacuo. The crude product was dissolved indichloromethane and adsorbed on teflon bulk sorbents. Purification overa silica gel cartridge (Rf200), eluting with a cyclohexane/ethyl acetategradient gave a mixture of the title compounds as a white solid. Mpt.140-142° C.

LCMS (method 1); Rt=1.17 min, [M+H] 583. ¹H NMR (400 MHz, CHLOROFORM-d)δ ppm 1.47 (t, J=7.5 Hz, 3 H); 3.94 (q, J=7.5 Hz, 2 H); 7.72-7.76 (m, 2H); 7.78-7.82 (m, 2 H); 3.94 (q, J=7.34 Hz, 2 H); 3.96 (s, 3 H); 8.92(s, 1 H); 9.01 (s, 1 H).

Example H52-(6-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Compound P15, Table P)

Step A: 3,6-dichloropyridine-2-carbonyl chloride

A sample of 3,6-dichloropyridine-2-carboxylic acid (5.00 g, 24.7 mmol)was diluted in dichloromethane (200 mL) and dimethylformamide (0.124 mL,1.6 mmol) was added. To this solution was added oxalyl chloride (3.15mL, 34.6 mmol) dropwise at room temperature over 10 min (gas evolution).The reaction mixture was stirred at room temperature, and after 2.5 h, afurther 1 ml oxalyl chloride was added and stirring continued for 1 hr.After this time, the reaction mixture was concentrated in vacuo and usedin the next step without further purification.

Step B:3,6-dichloro-N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamide

To a solution of N3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine (52.0g, 272 mmol) in tetrahydrofurane (260 mL) was added triethylamine (95.8mL, 680 mmol). The red solution was cooled to 0° C. and3,6-dichloropyridine-2-carbonyl chloride (51.5 g, 245 mmol) indichloromethane (156 mL) was added dropwise at 0-10° C. over 90 min. Theice-bath was removed after 1 h and the mixture was stirred at roomtemperature. LC-MS analysis showed mainly desired mass after 2 hours.The reaction mixture was stirred overnight and then washed with NH₄Clsat sol and the mixture was concentrated in vacuo to removetetrahydrofurane. The residue was then extracted with 1.2 Ldichloromethane (800 ml) ethylacetate and again 1 dichloromethane. Thecombined organic layers were dried over Na₂SO₄, filtered andconcentrated in vacuo to give the title compound as a brown solid.

LCMS (method 1): 366 (M+H⁺); retention time: 0.83 min.

Step C:2-(3,6-dichloro-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine

A yellow solution of3,6-dichloro-N-[5-(methylamino)-2-(trifluoromethyl)-4-pyridyl]pyridine-2-carboxamide(99.3 g, 272 mmol) in acetic acid (298 mL) was stirred at 110° C. bathtemperature for 16 hours. The reaction mixture was allowed to roomtemperature after which time LC-MS analysis showed desired mass. Toluenewas added and the mixture was concentrated in vacuo. To the residue wasadded cyclohexane and dichloromethane and the mixture obtained wasstirred under vacuum at 50° C. at 800 mbar. The slurry was furtherdiluted with cyclohexane and the solid filtered at the pump. The cakewas washed with cyclohexane (mixed with small amounts of DCM) and driedunder vacuum. Toluene was added the mixture was evaporated and driedunder vacuum at 60° C. and 20 mbar to remove traces of acetic acid,giving the title compound as a brown solid.

LCMS (method 1): 348 (M+H⁺); retention time: 0.95 min.

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm 4.04 (s, 3 H) 7.51 (d, J=8.44 Hz, 1H) 7.93 (d, J=8.44 Hz, 1 H) 8.19 (s, 1 H) 8.99 (s, 1 H)

Step D:2-(6-chloro-3-ethylsulfanyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine

A sample of2-(3,6-dichloro-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(1.14 g, 3.28 mmol) was dissolved in tetrahydrofurane under argon.Sodium ethanethiol (0.311 g, 3.28 mmol) was added portionwise at roomtemperature. The brown reaction mixture was stirred at room temperaturefor 2 hours by which time LC-MS analysis showed reaction completion withformation of the desired product. The reaction mixture was treated withNH₄Cl followed by water and ethyl acetate. The organic layer wasseparated, washed with water and brine, dried over Na₂SO₄, filtered andconcentrated in vacuo. The crude was purified by flash chromatographyover silica gel to give the title compound as a beige solid.

LCMS (method 1): 373 (M+H+); retention time: 1.02 min.

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.35 (t, J=7.34 Hz, 3 H) 2.97 (q,J=7.34 Hz, 2 H) 4.11 (s, 3 H) 7.44 (d, J=8.44 Hz, 1 H) 7.76 (d, J=8.44Hz, 1 H) 8.20 (d, J=0.73 Hz, 1 H) 8.97 (s, 1 H)

Step E:2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine

At 0° C. m-CPBA (2.35 g, 10.5 mmol) was added to a solution of2-(6-chloro-3-ethylsulfanyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(1.86 g, 4.99 mmol) in chloroform (46.5 mL). After the addition theice-bath was kept for 10 min and then the milky solution was allowed towarm to rt. The reaction mixture was stirred one night at roomtemperature. After this time a further portion of M-CPBA (1.12 g, 4.99mmol) was added the mixture was stirred 2 hours at room temperature.LC-MS analysis showed the complexion of the reaction. Saturated sodiumthiosulfate aqueous solution and sat NaHCO₃aq were added and the mixturestirred 1 hour. The organic layer was separated, extracted with NaHCO₃,dried over Na₂SO₄ and evaporated. The crude product was purified byflash chromatography over silica gel to give the title compound as awhite solid.

LCMS (method 1): 406 (M+H+); retention time: 0.95 min.

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.37 (t, J=7.34 Hz, 3 H) 3.79 (q,J=7.46 Hz, 2 H) 3.94 (s, 3 H) 7.75 (d, J=8.44 Hz, 1 H) 8.11 (s, 1 H)8.47 (d, J=8.44 Hz, 1 H) 9.00 (s, 1 H)

Step F:2-(6-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Compound P15, Table P)

In a supelco vial2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(0.40 g, 0.99 mmol) was dissolved in 1,4-dioxane (10 mL, 120 mmol).Cyclopropylboronic acid (0.18 g, 2.0 mmol) and potassium carbonate (0.41g, 3.0 mmol) were added and the mixture was purged with argon. Thentetrakis(triphenylphosphine) palladium (0.11 g, 0.099 mmol) was added,the vial was capped and the brown solution was heated at 100° C. for 19hours. LC-MS analysis showed the formation of desired product. Water andethyl acetate were added, the organic layer was separated, washed withbrine, dried over Na₂SO₄, filtered and concentrated in vacuo. The crudeobtained was purified by flash chromatography on silica gel. The mixtureobtained was dissolved in ethylacetate and washed again with NaHCO₃. Theorganic layer was washed with brine, dried over Na₂SO₄, filtered andevaporated. The solid obtained was purified again by reverse phase togive the title compound as a white solid.

LCMS (method 1): 411 (M+H⁺); retention time: 1.01 min.

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.11-1.13 (m, 1 H) 1.11-1.23 (m, 4H) 1.33 (t, J=7.34 Hz, 3 H) 2.22 (ddd, J=7.70, 4.77, 2.93 Hz, 1 H) 3.70(q, J=7.34 Hz, 2 H) 3.84 (s, 3 H) 7.54 (d, J=8.44 Hz, 1 H) 8.09 (s, 1 H)8.30 (d, J=8.44 Hz, 1 H) 8.97 (s, 1 H)

Example H62-[6-(3,5-difluorophenyl)-3-ethylsulfonyl-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Compound P8, Table P)

In a supelco vial,2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(100 mg, 0.2470 mmol), (3,5-difluorophenyl)boronic acid (46 mg, 0.2964mmol) and potassium carbonate (102 mg, 0.7411 mmol) were dissolved in1,4-dioxane (2.5 mL). The resulting mixture was flushed with argon over5 minutes. After this time, tetrakis(triphenylphosphine) palladium (28mg, 0.02470 mmol) was added and the vial was closed and heated at 95° C.for 16 hours. LC-MS analysis showed completion of the reaction. Thereaction mixture was cooled to room temperature and quenched with water.The aqueous layer was extracted with ethyl acetate. The combined organiclayers were washed with saturated solution of NaHCO₃ and saturated NaClsolution, dried over Na₂SO₄, filtered and concentrated in vacuo. Thecrude was purified by flash chromatography on silica gel to give thetitle compound as a yellow solid.

LCMS (method 1): 483 (M+H⁺); retention time: 1.09 min.

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.42 (t, J=7.34 Hz, 3 H) 3.84 (q,J=7.34 Hz, 2 H) 3.99 (s, 3 H) 7.00-7.05 (m, 1 H) 7.68 (d, J=5.87 Hz, 2H) 8.12 (d, J=8.44 Hz, 1 H) 8.17 (s, 1 H) 8.64 (d, J=8.44 Hz, 1 H) 9.06(s, 1 H)

Example H72-[3-ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]-2-pyridyl]-3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine(Compound P9, Table P)

Step A: Methyl3-ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]pyridine-2-carboxylate

To a stirred solution of methyl6-chloro-3-ethylsulfonyl-pyridine-2-carboxylate (526 mg, 2 mmol),3-(trifluoromethyl)-1H-pyrazole (1.361 g, 10 mmol) in dioxane (25 mL)was added CuI (38 mg, 0.2 mmol), N,N′-Dimethylethanediamine (880 mg, 1mmol) and potassium carbonate (1.38 g, 10 mmol). The reaction system wasrefluxed under a nitrogen atmosphere at 120° C. for 4 h. After coolingto room temperature, the reaction mixture was filtered and concentratedin vacuo. The crude product was purified by column chromatography onsilica gel to give the title compound.

1HNMR (400 MHz, CDCl₃): δppm 1.36 (t, 3 H), 3.49 (q, 2 H), 4.06 (s, 3H), 6.69 (s, 1 H), 8.26 (d, J=8.4 Hz, 1 H), 8.44 (d, J=8.4 Hz, 1 H),8.68 (s, 1 H); ESI-MS(+): 386 (M+Na)+

Step B:3-ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]pyridine-2-carboxylicacid

To a stirred solution of methyl3-ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]pyridine-2-carboxylate(218 mg, 0.6 mmol) in THF (10 mL) was added NaOH (120 mg, 3 mmol), andH₂O (30 ml). The reaction system was stirred at room temperature for 2h. TAfter this time, the pH value was adjusted to 2 with HCl and thereaction mixture extracted with ethyl acetate three times. The combinedorganic layers were dried over anhydrous sodium sulfate, filtered andconcentrated in vacuo to give the title compound.

1HNMR (400 MHz, DMSO-d6): δppm 1.18 (t, 3 H), 3.54 (q, 2 H), 7.12 (s, 1H), 8.21 (d, J=8.8 Hz, 1 H), 8.53 (d, J=8.4 Hz, 1 H), 8.86 (s, 1 H);ESI-MS(+): 348 (M−H)−

Step C:2-[3-ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]-2-pyridyl]-3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine(Compound P9, Table P)

To a stirred solution of3-ethylsulfonyl-6-[3-(trifluoromethyl)pyrazol-1-yl]pyridine-2-carboxylicacid (180 mg, 0.52 mmol),N3-methyl-6-(trifluoromethylsulfanyl)pyridine-3,4-diamine (250 mg, 1.11mmol) and HATU (0.78 g, 2 mmol) in DMF (30 mL) was added DIPEA (2 ml, 10mmol). The reaction mixture was stirred at room temperature overnight.The reaction mixture was then diluted with ethyl acetate and H₂O, theorganic layer was washed with brine, dried over anhydrous sodiumsulfate, filtered and concentrated in vacuo. The crude product was usedfor the next step without further purification. The solution of thecrude product in acetic acid (20 mL) was refluxed at 120° C. for 24 h.The reaction mixture was then evaporated to dryness. The residue waspurified by chromatography on silica gel (petroleum: EtOAc=4:1) toafford the title compound as white solid.

LCMS (method 1): 537 (M+H⁺); retention time: 1.17 min.

1HNMR (400 MHz, CDCl3): δ (ppm) 1.37 (t, 3 H), 3.73 (q, 2 H), 3.90 (s, 3H), 6.79 (s, 1H), 8.14 (s, 1 H), 8.45 (d, J=4.8 Hz, 1 H), 8.65 (s, 1 H),8.67 (d, J=4.8 Hz, 1 H), 8.98(s, 1 H); 19FNMR (376 MHz, CDCl3): δ (ppm)−46.40 (s, 3 F), −68.19 (s, 3 F)

Example 2(3-ethylsulfonyl-6-pyrimidin-2-yl-2-pyridyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine(Compound P10, Table P)

Step A: N-methyl-4-nitro-6-(trifluoromethylsulfanyl)pyridin-3-amine

A sample of (bpy)CuSCF₃ (14.4 g, 45 mmol) and6-bromo-N-methyl-4-nitro-pyridin-3-amine (6.96 g, 30 mmol) in 120 ml ofCH₃CN was refluxed for 48 h under nitrogen. The reaction mixture wasremoved from the oil bath and allowed to cool to room temperature, andthen filtered through SiO2. The silica gel was eluted with diethylether, and concentrated in vacuo. The residue was purified by silica gelcolumn chromatography to give the title compound.

1HNMR (400 MHz, DMSO-d6): δ (ppm) 3.10 (d, J=5.2 Hz, 3 H), 8.21 (s, 1 H)8.49 (q, 1 H), 8.67 (s, 1 H); 19FNMR (376 MHz, DMSO-d6): δ (ppm) −36.79(s, 3 F); ESI-MS: 252 (M−H)−.

Step B: N3-methyl-6-(trifluoromethylsulfanyl)pyridine-3,4-diamine

To a solution ofN-methyl-4-nitro-6-(trifluoromethylsulfanyl)pyridin-3-amine (3.42 g,13.5 mmol) in methanol (50 mL) was added Raney Ni (20% wt). To thismixtures was added hydrazine hydrate (10 mL) dropwise at roomtemperature. The reaction mixture was stirred at room temperature for 30minutes. Raney Ni was filtered off through celite; the filtrate wasdried in vacuo and purified with chromatography column on silica gel toafford the title compound as white solid.

1HNMR (400 MHz, DMSO-d6): δppm 2.78 (d, J=5.2 Hz, 3 H), 5.20 (q, 1 H),5.77 (s, 2 H), 6.82 (s, 1 H), 7.53 (s, 1 H); 19FNMR (376 MHz, DMSO-d6):δppm −45.49 (s, 3 F); ESI-MS(+): 224 (M+H)+.

Step C: Methyl 3,6-dichloropyridine-2-carboxylate

To a solution of 3,6-dichloropyridine-2-carboxylic acid (76.8 g, 0.4mol) in methanol (500 mL) was added SOCl2 (150 ml) dropwise at roomtemperature. The reaction mixture was stirred at room temperature for 3hours. After this time, the reaction mixture was poured into water andextracted with ethyl acetate three times. The combined organic layerswere dried over sodium sulfate, filtered and concentrated in vacuo togive the title compound.

1HNMR (400 MHz, DMSO-d6): δppm 3.90 (s, 3 H), 7.80 (d, J=8.8 Hz, 1 H),8.20 (d, J=8.8 Hz, 1 H); ESI-MS(+): 228 (M+Na)+.

Step D: Methyl 6-chloro-3-ethylsulfanyl-pyridine-2-carboxylate

To a solution of methyl 3,6-dichloropyridine-2-carboxylate (16 g, 77.6mmol) in DMF (150 mL) was added sodium ethanethiolate (7.2 g, 85.8 mmol)at 0° C. After the addition, the reaction mixture was stirred at roomtemperature for 30 min. LCMS analysis after this time showed reactioncompletion. The reaction mixture was poured into water, and precipitateformed filtered and dried under an infrared oven to afford the titlecompound as white solid.

1HNMR (400 MHz, CDCl3): δppm 1.38 (t, 3 H), 2.92 (q, 2 H), 3.98 (s, 3H),7.40 (d, J=8.8 Hz, 1 H), 7.66 (d, J=8.8 Hz, 1 H); ESI-MS(+): 254(M+Na)+.

Step E: Methyl 6-chloro-3-ethylsulfonyl-pyridine-2-carboxylate

A solution of methyl 6-chloro-3-ethylsulfanyl-pyridine-2-carboxylate(11.55 g, 50 mmol) and m-CPBA (25.8 g, 150 mmol) in 200 ml ofdichloromethane was stirred at room temperature for 2 hours. After thistime, the mixture was poured into a saturated solution of NaHCO₃ andNa₂SO₃, and extracted with DCM three times. The combined organic layerswere dried over sodium sulfate, filtered and concentrated in vacuo Thecrude product was purified by column chromatography on silica gel togive the title compound.

1HNMR (400 MHz, CDCl3): δppm 1.33 (t, 3 H), 3.51 (q, 2 H), 4.02 (s, 3H), 7.63 (d, J=8 Hz, 1 H), 8.29 (d, J=8 Hz, 1 H); ESI-MS(+): 286(M+Na)+.

Step F: Methyl 3-ethylsulfonyl-6-pyrimidin-2-yl-pyridine-2-carboxylate

To a stirred solution of methyl6-chloro-3-ethylsulfonyl-pyridine-2-carboxylate (526 mg, 2 mmol) andtributyl(pyrimidin-2-yl)stannane (1.107 g, 3 mmol) in dioxane (25 mL)were added CuI (76 mg, 0.4 mmol) and PdCl2(PPh3)2 (140 mg, 0.2 mmol).The reaction mixture was refluxed under an nitrogen atmosphere at 120°C. for 4 hours. After cooling to room temperature, the reaction mixturewas filtered and concentrated in vacuo. The crude product was purifiedby column chromatography on silica gel to give the title compound.

1HNMR (400 MHz, CDCl3): δppm 1.36 (t, 3 H), 3.58 (q, 2 H), 4.05 (s, 3H), 7.42 (t, 1 H), 8.53 (d, J=8.4 Hz, 1 H), 8.81 (d, J=8.4 Hz, 1 H),9.00 (d, J=4.8 Hz, 2 H); ESI-MS(+): 330 (M+Na)+

Step G: 3-ethylsulfonyl-6-pyrimidin-2-yl-pyridine-2-carboxylic acid

To a stirred solution of methyl3-ethylsulfonyl-6-pyrimidin-2-yl-pyridine-2-carboxylate (522 mg, 1.7mmol) in tetrahydrofurane (10 mL) was added NaOH (340 mg, 8.5 mmol) andwater (30 ml). The reaction system was stirred at room temperature for 2hours, by which time LCMS analysis showed reaction completion. The pHvalue was adjusted to 2 with HCl, and the reaction mixture was extractedwith ethyl acetate three times. The organic layers were dried overanhydrous sodium sulfate, filtered and concentrated in vacuo to give thetitle compound.

1HNMR (400 MHz, DMSO-d6): δppm 1.22 (t, 3 H), 3.57 (q, 2 H), 7.66 (m,1H), 7.68 (d J=4.8 Hz, 1 H), 8.55 (d, J=8.4 Hz, 1 H), 8.70 (d, J=8.4 Hz,1 H), 9.07 (d, J=4.8 Hz, 2 H).

Step H:2-(3-ethylsulfonyl-6-pyrimidin-2-yl-2-pyridyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine(Compound P10, Table P)

To a stirred solution of3-ethylsulfonyl-6-pyrimidin-2-yl-pyridine-2-carboxylic acid (470 mg, 1.6mmol), N3-methyl-6-(trifluoromethylsulfanyl)pyridine-3,4-diamine (430mg, 1.92 mmol) and HATU (1.216 g, 3.2 mmol) in DMF (30 mL) was addedDIPEA (2.8 ml, 16 mmol). The reaction system was stirred at roomtemperature overnight. After this time the reaction mixture was dilutedwith ethyl acetate and H₂O, and the organic layer washed with brine,dried over anhydrous sodium sulfate, and concentrated in vacuo. Thecrude product was used for the next step without further purification.

A solution of the crude product in acetic acid (20 mL) was refluxed at120° C. for 24 h. The reaction mixture was evaporated to dryness and theresidue purified by chromatography on silica gel to afford the titlecompound as white solid.

LCMS (method 1): 481 (M+H+); retention time: 0.93 min

1HNMR (400 MHz, CDCl3): δ (ppm) 1.38 (t, 3 H), 3.80 (q, 2 H), 3.93 (s, 3H), 7.44 (t, 1H), 8.10 (s, 1 H), 8.70 (d, J=8.4 Hz, 1 H), 8.96 (m, 2 H),9.0 (d, J=4.8 Hz, 2 H); 19FNMR (376 MHz, CDCl3): δ (ppm) −45.77 (s, 3F);

Example H82-(6-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine(Compound P13, Table P)

Step A: Methyl 6-cyclopropyl-3-ethylsulfanyl-pyridine-2-carboxylate

To a stirred solution of methyl6-chloro-3-ethylsulfanyl-pyridine-2-carboxylate (462 mg, 2 mmol),cyclopropylboronic acid (344 mg, 4 mmol) in dioxane (25 mL) was addedpotassium carbonate (552 mg, 4 mmol) and Pd(PPh3)4 (230 mg, 0.2 mmol).The reaction system was refluxed under an nitrogen atmosphere at 120° C.for 24 hours. After cooling to room temperature, the reaction mixturewas filtered and concentrated in vacuo. The crude product was purifiedby column chromatography on silica gel to give the title compound.

1HNMR (400 MHz, CDCl3): δ (ppm) 0.98 (m, 4 H), 1.32 (t, 3 H), 2.08(m, 1H), 2.88 (q, 2 H), 3.95 (s, 3 H), 7.08 (d, J=8.4 Hz, 1 H), 7.57 (d, J=8Hz, 1 H); ESI-MS(+): 260 (M+Na)+.

Step B: 6-cyclopropyl-3-ethylsulfanyl-pyridine-2-carboxylic acid

To a stirred solution of methyl6-cyclopropyl-3-ethylsulfanyl-pyridine-2-carboxylate (320 mg, 1.35 mmol)in THF (10 mL) was added NaOH (280 mg, 7 mmol) and H₂O (30 ml). Thereaction system was stirred at room temperature for 4 hours. The pHvalue was adjusted to 2 with HCl., and the reaction mixture extractedwith ethyl acetate three times. The combined organic layers dried overanhydrous sodium sulfate, filtered and concentrated in vacuo to give thetitle compound.

1HNMR (400 MHz, DMSO-d6): δppm 0.93 (m, 4 H), 1.18 (t, 3 H), 2.07 (m, 1H), 2.91 (q, 2 H) , 7.36 (d, J=8.0 Hz, 1 H), 7.73 (d, J=8.4 Hz, 1 H),12.93 (bs, 1 H); ESI-MS(−): 222 (M−H)−.

Step C:6-bromo-2-(6-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-3-methyl-imidazo[4,5-c]pyridine

To a stirred solution of6-cyclopropyl-3-ethylsulfanyl-pyridine-2-carboxylic acid (280 mg, 1.25mmol), 6-bromo-N3-methyl-pyridine-3,4-diamine (303 mg, 1.5 mmol) andHATU (0.78 g, 2 mmol) in DMF (30 mL) was added DIPEA (2 ml, 10 mmol).The reaction mixture was stirred at room temperature overnight. Thereaction mixture was then diluted with ethyl acetate and H₂O, and theorganic layer washed with brine, dried over anhydrous sodium sulfate,filtered and concentration in vacuo. The crude product was used for thenext step without further purification. A solution of the crude productin acetic acid (20 mL) was refluxed at 120° C. for 24 h. The reactionmixture was concentrated, and purified by column chromatography onsilica gel and purified to afford the title compound as white solid.

1HNMR (400 MHz, CDCl3): δ (ppm) 1.04 (m, 4 H), 1.31 (t, 3 H), 2.1 (m, 1H), 2.91 (q, 2 H), 3.92 (s, 3 H), 7.25 (d, J=8.4 Hz, 1 H), 7.66 (d, J=8Hz, 1 H), 7.94 (s, 1 H), 8.62 (s, 1H); ESI-MS(+): 413 (M+Na)+.

Step D:6-bromo-2-(6-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-3-methyl-imidazo[4,5-c]pyridine(Compound P12, Table P)

A sample of6-bromo-2-(6-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-3-methyl-imidazo[4,5-c]pyridine(285 mg, 0.73 mmol) and m-CPBA (630 mg, 3.66 mmol) in 40 ml of DCM wasstirred at room temperature for 2 hours. Then the mixture was pouredinto a saturated solution of NaHCO₃ and Na₂SO₃ in water, and extractedwith dichloromethane three times. The combined organic layers were driedover sodium sulfate, filtered and concentrated in vacuo. The crudeproduct was purified by column chromatography on silica gel to give thetitle compound.

LCMS (method 1): 421/423 (M+H⁺); retention time: 0.97 min

1HNMR (400 MHz, CDCl3): δ (ppm) 1.16 (m, 4 H), 1.34 (t, 3 H), 2.05 (m, 1H), 3.69 (q, 2 H), 3.76 (s, 3 H), 7.53 (d, J=8.0 Hz, 1 H), 7.86 (s, 1H), 8.30 (d, J=8.4 Hz, 1 H), 8.66 (s, 1H);

Step E:2-(6-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethylsulfanyl)imidazo[4,5-c]pyridine(Compound P13, Table P)

A sample of (bpy)CuSCF3 (410 mg, 1.28 mmol) and6-bromo-2-(6-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-3-methyl-imidazo[4,5-c]pyridine(270 mg, 0.64 mmol) in 20 ml of CH3CN was refluxed for 48 hours undernitrogen. The reaction mixture was removed from the oil bath and allowedto cool, and filtered through SiO2, eluting with diethyl ether. Thefiltrate was washed with brine, and concentrated in vacuo. The residuewas purified by silica gel column chromatography to give the titlecompound.

LCMS (method 1): 444 (M+H⁺); retention time: 1.07 min

1HNMR (400 MHz, CDCl3): δ (ppm) 1.19(m, 4 H), 1.34 (t, 3 H), 2.12 (m, 1H), 3.71 (q, 2 H), 3.81 (s, 3 H), 7.54 (d, J=8.4 Hz, 1 H), 8.10 (s, 1H), 8.31 (d, J=8.8 Hz, 1 H), 8.92 (s, 1H)

Example H96-(6-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazine(Compound P22, Table P)

Step A: 3-chloro-6-iodopyridazine

Hydriodic acid (250 mL) was added to a mixture of 3,6-dichloropyridazine(149 g, 1 mol) and NaI (180 g, 1.2 mol) in 500 mL of CHCl₃. After theaddition, the mixture was stirred at ambient temperature for 24 h, andpoured into water and extracted with dichloromethane three times. Thecombined organic layers were dried over sodium sulfate, filtered andconcentrated in vacuo to give the title compound.

¹H-NMR (400 Mz, DMSO-d₆) δ: 7.63 (d, 1H), 8.16 (d, 1H).

Step B: 3-chloro-6-(trifluoromethyl)pyridazine

TMSCF₃ (198.8 g, 1.4 mol) was added to a mixture of3-chloro-6-iodopyridazine (240 g, 1 mol), KF (81 g, 1.4 mol) and CuI(228 g, 1.2 mol) in 1 L of DMF under nitrogen. After the addition, themixture was stirred at 50° C. for 2 h. The mixture was then poured intowater and extracted with ether (three times). The combined organiclayers were dried over sodium sulfate, filtered and concentrated invacuo. The residue was purified by flash column chromatography on silicagel to give the title compound.

¹H-NMR (400 Mz, DMSO-d₆) δ: 8.30 (d, 1H), 8.38 (d, 1H); ¹⁹F-NMR (400 Mz,DMSO-d₆) δ: −64.93 (s, 3F).

Step C: N-methyl-6-(trifluoromethyl)pyridazin-3-amine

A solution of MeNH₂ (100 g, 30% in EtOH) was added to a mixture of3-chloro-6-(trifluoromethyl) pyridazine (91 g, 0.5 mol) in 100 ml ofEtOH. After the addition, the mixture was stirred at 50° C. for 2 hoursand then poured into water. The precipitated solid was filtered anddried in vacuum to give the title compound

¹H-NMR (400 Mz, DMSO-d₆) δ: 2.93 (d, 3H), 6.95 (d, 1H), 7.58 (q, 1H),7.63 (d, 1H); ¹⁹F-NMR (400 Mz, DMSO-d₆) δ: −59.88 (s, 3F); ESI-MS(+):178 (M+H)⁺.

Step D: 4-bromo-N-methyl-6-(trifluoromethyl)pyridazin-3-amine

Bromine (32 g, 0.2 mol) was added to a mixture ofN-methyl-6-(trifluoromethyl) pyridazin-3-amine (17.7 g, 0.1 mol) in 100mL of MeCN. After the addition, the mixture was stirred at ambienttemperature for 48 hours. After this time, the mixture was poured intoammonium hydroxide (10% solution) and extracted with ethyl acetate(three times). The combined organic layers were dried over sodiumsulfate, filtered and concentrated in vacuo. The residue was purified byflash column chromatography on silica gel to give the title compound.

¹H-NMR (400 Mz, DMSO-d₆) δ: 3.03 (d, 3H), 7.45 (q, 1H), 8.23 (s, 1H);¹⁹F-NMR (400 Mz, DMSO-d₆) δ: −59.47 (s, 3F); ESI-MS(+): 256/258 (M+H)⁺.

Step E: N³-methyl-6-(trifluoromethyl)pyridazine-3,4-diamine

4-Bromo-N-methyl-6-(trifluoromethyl)pyridazin-3-amine (3 g, 11.8 mmol)and 120 mL of ammonium hydroxide was placed in a 250 mL autoclave. Then,nitrogen gas was introduced to the autoclave and pressure was increasedto 2 MPa. The mixture was stirred at 130° C. for 48 h, poured into waterand extracted with ethyl acetate (three times). The combined organiclayers were dried over sodium sulfate, filtered and concentrated invacuo. The residue was purified by column chromatography on silica gelto give the title compound

¹H-NMR (400 Mz, DMSO-d₆) δ: 297(d, 3H), 6.27 (s, 2H), 6.50 (q, 1H), 6.67(s, 1H); ¹⁹F-NMR (400 Mz, DMSO-d₆) δ: −61.96 (s, 3F); ESI-MS(+): 193(M+H)⁺.

Step F: 6-cyclopropyl-3-ethylsulfanyl-pyridine-2-carbonyl chloride

Oxalyl chloride (380 mg, 3 mmol) was added to a mixture of6-cyclopropyl-3-ethylsulfanyl-pyridine-2-carboxylic acid (223 mg, 1mmol) in 10 mL of dichloromethane and stirred at room temperature for 30min. The excess oxalyl chloride and dichloromethane was removed underreduced pressure to give the title compound in almost quantitative yield(241 mg). The crude title compound was directly used for the next stepwithout further purification.

Step G:6-(6-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazine(Compound P22, Table P)

A sample of 6-cyclopropyl-3-ethylsulfanyl-pyridine-2-carbonyl chloride(241 mg, 1 mmol) was added to a mixture of N3-methyl-6-(trifluoromethyl)pyridazine-3,4-diamine (211 mg, 1.1 mmol) in 20 mL of THF and themixture was reflux for 48 hours. After this time, the mixture was pouredinto water and extracted with ethyl acetate three times. The combinedorganic layers were dried over sodium sulfate, filtered and concentratedin vacuo. The crude product was purified by column chromatography onsilica gel to give the title compound.

1H NMR (400 MHz, DMSO) δ 0.97-1.00 (m, 2H), 1.02-1.07 (m, 2H), 1.19 (t,3H), 2.22-2.28 (m, 1H), 2.98 (q, 2H), 4.08 (s, 3H), 7.58 (d, 1H), 7.98(d, 1H), 8.71 (s, 1H); 19F NMR (400 MHz, DMSO) δ −62.23 (s, 3F);ESI-MS(+): 380 (M+H)+, 434 (M+Na+MeOH)+.

Example H106-(6-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazine(Compound P14, Table P)

A solution of6-(6-cyclopropyl-3-ethylsulfanyl-2-pyridyl)-7-methyl-3-(trifluoromethyl)imidazo[4,5-c]pyridazine(70 mg, 0.18 mmol) and m-CPBA (93 mg, 0.54 mmol) in 10 ml ofdichloromethane was stirred at room temperature for 2 hours. The mixturewas then poured into a saturated solution of NaHCO₃ and Na₂SO₃ in water,and extracted with ethyl acetate three times. The combined organiclayers were dried over sodium sulfate, filtered and concentrated invacuo. The crude product was purified by column chromatography on silicagel to give the title compound.

LCMS (method 1): 413 (M+H⁺); retention time: 1.01 min.

1H NMR (400 MHz, DMSO-d6) δ 1.05-1.07 (m, 2H), 1.13-1.18 (m, 2H), 1.15(t, 3H), 2.38-2.42 (m, 1H), 3.63 (q, 2H), 3.88 (s, 3H), 7.88 (d, 1H),8.34 (d, 1H), 8.72 (s, 1H); 19F-NMR (400 Mz, DMSO-d6) δ: −64.55 (s, 3F);

Example H112-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-2-pyridyl]acetonitrile(Compound P23, Table P)

In a microwave vial2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(0.20 g, 0.49 mmol) was dissolved in DMF (1.0 mL). The vial was flushedwith argon and TMSCN (0.10 mL, 0.74 mmol), difluorozinc (0.031 g, 0.30mmol), Pd₂(dba)₃ (0.0091 g, 0.0099 mmol) and XANTPHOS (0.012 g, 0.020mmol) were added. The vial was capped and heated in the microwave at140° C. for 30 min. The reaction mixture was diluted with ethyl acetateand filtered over hyflo. The filtrate was extracted with water andbrine, dried over Na₂SO₄, filtered and concentrated in vacuo. The crudeproduct was purified by flash chromatography on silica gel to give thetitle compound.

LCMS (method 1): 410 (M+H+); retention time: 0.84 min.

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.40 (t, J=7.52 Hz, 3 H) 3.83 (q,J=7.34 Hz, 2 H) 3.97 (s, 3 H) 4.17 (s, 2 H) 7.89 (d, J=8.44 Hz, 1 H)8.15 (s, 1 H) 8.63 (d, J=8.07 Hz, 1 H) 9.04 (s, 1 H)

Example H121-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-2-pyridyl]cyclopropanecarbonitrile(Compound P17, Table P)

A sample of2-[5-ethylsulfonyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-2-pyridyl]acetonitrile(0.11 g, 0.27 mmol) was dissolved in acetonitrile (2.8 mL). Cesiumcarbonate (0.27 g, 0.81 mmol) was added followed by adding1,2-dibromoethane (0.047 mL, 0.54 mmol). The mixture was stirred at 80°C. for 1 hour. LC-MS analysis showed consumption of the startingmaterial and mass of desired product. The reaction was quenched withwater and acetonitrile and the evaporated. The residue was diluted withethyl acetate washed with water and brine, dried over Na₂SO₄, filteredand concentrated in vacuo. The crude product was purified by flashchromatography on silica gel to give the title compound

LCMS (method 1): 436 (M+H+); retention time: 0.94 min.

1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.38 (t, J=7.52 Hz, 3 H) 1.88-2.02(m, 4 H) 3.73 (d, J=7.70 Hz, 2 H) 3.86 (s, 3 H) 8.12-8.19 (m, 2 H) 8.54(d, J=8.44 Hz, 1 H) 9.02 (s, 1 H)

Example H132-[3-ethylsulfonyl-6-[2-(3-fluorophenyl)ethynyl]-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(Compound P20, Table P)

A sample of2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine(0.10 g, 0.25 mmol), 1-ethynyl-3-fluoro-benzene (0.044 mL, 0.37 mmol),DIPEA (0.086 mL, 0.49 mmol), copper(I)iodide (0.0024 g, 0.012 mmol) intetrahydrofurane (4.0 mL) were mixed in a vial and the clear, paleyellow solution was flushed with argon. PdCl₂(PPH₃)₂ (0.0088 g, 0.012mmol) was added and the mixture was stirred at room temperatureovernight. Reaction after this time showed completion. The crude mixturewas purified by flash chromatography to give the title compound as abeige solid.

LCMS (method 1): 489 (M+H⁺); retention time: 1.11 min.

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.39 (t, J=7.34 Hz, 3 H) 3.78 (q,J=7.46 Hz, 2 H) 3.96 (s, 3 H) 7.14-7.24 (m, 1 H) 7.32-7.38 (m, 1 H)7.37-7.48 (m, 2 H) 7.92 (d, J=8.44 Hz, 1 H) 8.14 (s, 1 H) 8.54 (d,J=8.44 Hz, 1 H) 9.02 (s, 1 H)

Compounds in tables 1-88 can be prepared analogously to the methodsdescribed above.

TABLE P Examples of compounds of formula (I) Compound Melting No.Compound Point MS/NMR P1

255-256 LCMS (method 1): 481/483 (M + H)⁺ R_(t) = 1.11 min P2

— LCMS (method 1): 541 (M + H)⁺ Rt = 1.14 min 1.14 min, (M + H) = 541 P3

261-263 LCMS (method 1): 505 (M + H)⁺ R_(t) = 1.07 min P4

140-142 LCMS (method 1): 583 (M + H)⁺ R_(t) = 1.17 min P5

170-172 LCMS (method 1): 583 (M + H)⁺ R_(t) = 1.17 min P6

118-128 LCMS (method 1): 549/551 (M + H)⁺ R_(t) = 1.14 min P7

289-291 LCMS (method 1): 533/535/537 (M + H)⁺ R_(t) = 1.20 min P8

223-225 LCMS (method 1): 483 (M + H)⁺ R_(t) = 1.10 min P9

201-202 LCMS (method 1): 537 (M + H)⁺ R_(t) = 1.17 min P10

180-181 LCMS (method 1): 481 (M + H)⁺ R_(t) = 0.93 min P11

200-201 LCMS (method 1): 503/505 (M + H)⁺ R_(t) = 1.14 min P12

194-195 LCMS (method 1): 421/423 (M + H)⁺ R_(t) = 0.97 min P13

130-131 LCMS (method 1): 444 (M + H)⁺ R_(t) = 1.07 P14

150-152 LCMS (method 1): 444 (M + H)⁺ R_(t) = 1.01 min P15

185-187 LCMS (method 1): 413 (M + H)⁺ R_(t) = 1.01 min P16

— LCMS (method 1): 438 (M + H)⁺ R_(t) = 0.86 min P17

— LCMS (method 1): 436 (M + H)⁺ R_(t) = 0.95 min P18

— LCMS (method 1): 465 (M + H)⁺ R_(t) = 1.07 min P19

— LCMS (method 1): 507 (M + H)⁺ R_(t) = 1.12 min P20

— LCMS (method 1): 489 (M + H)⁺ R_(t) = 1.10 min P21

— LCMS (method 1): 472/474 (M + H)⁺ R_(t) = 0.94 min P22

— 1H NMR (400 MHz, DMSO) δ 0.97-1.00 (m, 2H), 1.02-1.07 (m, 2H), 1.19(t, 3H), 2.22-2.28 (m, 1H), 2.98 (q, 2H), 4.08 (s, 3H), 7.58 (d, 1H),7.98 (d, 1H), 8.71 (s, 1H P23

LCMS (method 1): 410 (M + H)⁺ R_(t) = 0.84 min

The activity of the compositions according to the invention can bebroadened considerably, and adapted to prevailing circumstances, byadding other insecticidally, acaricidally and/or fungicidally activeingredients. The mixtures of the compounds of formula I with otherinsecticidally, acaricidally and/or fungicidally active ingredients mayalso have further surprising advantages which can also be described, ina wider sense, as synergistic activity. For example, better tolerance byplants, reduced phytotoxicity, insects can be controlled in theirdifferent development stages or better behaviour during theirproduction, for example during grinding or mixing, during their storageor during their use.

Suitable additions to active ingredients here are, for example,representatives of the following classes of active ingredients:organophosphorus compounds, nitrophenol derivatives, thioureas, juvenilehormones, formamidines, benzophenone derivatives, ureas, pyrrolederivatives, carbamates, pyrethroids, chlorinated hydrocarbons,acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoidsand Bacillus thuringiensis preparations.

The following mixtures of the compounds of formula I with activeingredients are preferred (the abbreviation “TX” means “one compoundselected from the group consisting of the compounds described in Tables1 to 88 and P of the present invention”):

an adjuvant selected from the group of substances consisting ofpetroleum oils (628)+TX,

an acaricide selected from the group of substances consisting of1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910)+TX,2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name)(1059)+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name)(1295)+TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981)+TX,abamectin (1)+TX, acequinocyl (3)+TX, acetoprole [CCN]+TX, acrinathrin(9)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, alpha-cypermethrin(202)+TX, amidithion (870)+TX, amidoflumet [CCN]+TX, amidothioate(872)+TX, amiton (875)+TX, amiton hydrogen oxalate (875)+TX, amitraz(24)+TX, aramite (881)+TX, arsenous oxide (882)+TX, AVI 382 (compoundcode)+TX, AZ 60541 (compound code)+TX, azinphos-ethyl (44)+TX,azinphos-methyl (45)+TX, azobenzene (IUPAC name) (888)+TX, azocyclotin(46)+TX, azothoate (889)+TX, benomyl (62)+TX, benoxafos [CCN]+TX,benzoximate (71)+TX, benzyl benzoate (IUPAC name) [CCN]+TX, bifenazate(74)+TX, bifenthrin (76)+TX, binapacryl (907)+TX, brofenvalerate+TX,bromocyclen (918)+TX, bromophos (920)+TX, bromophos-ethyl (921)+TX,bromopropylate (94)+TX, buprofezin (99)+TX, butocarboxim (103)+TX,butoxycarboxim (104)+TX, butylpyridaben+TX, calcium polysulfide (IUPACname) (111)+TX, camphechlor (941)+TX, carbanolate (943)+TX, carbaryl(115)+TX, carbofuran (118)+TX, carbophenothion (947)+TX, CGA 50'439(development code) (125)+TX, chinomethionat (126)+TX, chlorbenside(959)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorfenapyr (130)+TX, chlorfenethol (968)+TX, chlorfenson (970)+TX,chlorfensulfide (971)+TX, chlorfenvinphos (131)+TX, chlorobenzilate(975)+TX, chloromebuform (977)+TX, chloromethiuron (978)+TX,chloropropylate (983)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl(146)+TX, chlorthiophos (994)+TX, cinerin I (696)+TX, cinerin II(696)+TX, cinerins (696)+TX, clofentezine (158)+TX, closantel [CCN]+TX,coumaphos (174)+TX, crotamiton [CCN]+TX, crotoxyphos (1010)+TX, cufraneb(1013)+TX, cyanthoate (1020)+TX, cyflumetofen (CAS Reg. No.:400882-07-7)+TX, cyhalothrin (196)+TX, cyhexatin (199)+TX, cypermethrin(201)+TX, DCPM (1032)+TX, DDT (219)+TX, demephion (1037)+TX, demephion-O(1037)+TX, demephion-S (1037)+TX, demeton (1038)+TX, demeton-methyl(224)+TX, demeton-O (1038)+TX, demeton-O-methyl (224)+TX, demeton-S(1038)+TX, demeton-S-methyl (224)+TX, demeton-S-methylsulfon (1039)+TX,diafenthiuron (226)+TX, dialifos (1042)+TX, diazinon (227)+TX,dichlofluanid (230)+TX, dichlorvos (236)+TX, dicliphos+TX, dicofol(242)+TX, dicrotophos (243)+TX, dienochlor (1071)+TX, dimefox (1081)+TX,dimethoate (262)+TX, dinactin (653)+TX, dinex (1089)+TX, dinex-diclexine(1089)+TX, dinobuton (269)+TX, dinocap (270)+TX, dinocap-4 [CCN]+TX,dinocap-6 [CCN]+TX, dinocton (1090)+TX, dinopenton (1092)+TX, dinosulfon(1097)+TX, dinoterbon (1098)+TX, dioxathion (1102)+TX, diphenyl sulfone(IUPAC name) (1103)+TX, disulfiram [CCN]+TX, disulfoton (278)+TX, DNOC(282)+TX, dofenapyn (1113)+TX, doramectin [CCN]+TX, endosulfan (294)+TX,endothion (1121)+TX, EPN (297)+TX, eprinomectin [CCN]+TX, ethion(309)+TX, ethoate-methyl (1134)+TX, etoxazole (320)+TX, etrimfos(1142)+TX, fenazaflor (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide(330)+TX, fenothiocarb (337)+TX, fenpropathrin (342)+TX, fenpyrad+TX,fenpyroximate (345)+TX, fenson (1157)+TX, fentrifanil (1161)+TX,fenvalerate (349)+TX, fipronil (354)+TX, fluacrypyrim (360)+TX,fluazuron (1166)+TX, flubenzimine (1167)+TX, flucycloxuron (366)+TX,flucythrinate (367)+TX, fluenetil (1169)+TX, flufenoxuron (370)+TX,flumethrin (372)+TX, fluorbenside (1174)+TX, fluvalinate (1184)+TX, FMC1137 (development code) (1185)+TX, formetanate (405)+TX, formetanatehydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX,gamma-HCH (430)+TX, glyodin (1205)+TX, halfenprox (424)+TX, heptenophos(432)+TX, hexadecyl cyclopropanecarboxylate (IUPAC/Chemical Abstractsname) (1216)+TX, hexythiazox (441)+TX, iodomethane (IUPAC name)(542)+TX, isocarbophos (473)+TX, isopropylO-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX,ivermectin [CCN]+TX, jasmolin I (696)+TX, jasmolin II (696)+TX,jodfenphos (1248)+TX, lindane (430)+TX, lufenuron (490)+TX, malathion(492)+TX, malonoben (1254)+TX, mecarbam (502)+TX, mephosfolan (1261)+TX,mesulfen [CCN]+TX, methacrifos (1266)+TX, methamidophos (527)+TX,methidathion (529)+TX, methiocarb (530)+TX, methomyl (531)+TX, methylbromide (537)+TX, metolcarb (550)+TX, mevinphos (556)+TX, mexacarbate(1290)+TX, milbemectin (557)+TX, milbemycin oxime [CCN]+TX, mipafox(1293)+TX, monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin[CCN]+TX, naled (567)+TX, NC-184 (compound code)+TX, NC-512 (compoundcode)+TX, nifluridide (1309)+TX, nikkomycins [CCN]+TX, nitrilacarb(1313)+TX, nitrilacarb 1:1 zinc chloride complex (1313)+TX, NNI-0101(compound code)+TX, NNI-0250 (compound code)+TX, omethoate (594)+TX,oxamyl (602)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp′-DDT(219)+TX, parathion (615)+TX, permethrin (626)+TX, petroleum oils(628)+TX, phenkapton (1330)+TX, phenthoate (631)+TX, phorate (636)+TX,phosalone (637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosphamidon(639)+TX, phoxim (642)+TX, pirimiphos-methyl (652)+TX,polychloroterpenes (traditional name) (1347)+TX, polynactins (653)+TX,proclonol (1350)+TX, profenofos (662)+TX, promacyl (1354)+TX, propargite(671)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion(1360)+TX, prothoate (1362)+TX, pyrethrin I (696)+TX, pyrethrin II(696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, quinalphos(711)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX,RA-17 (development code) (1383)+TX, rotenone (722)+TX, schradan(1389)+TX, sebufos+TX, selamectin [CCN]+TX, SI-0009 (compound code)+TX,sophamide (1402)+TX, spirodiclofen (738)+TX, spiromesifen (739)+TX,SSI-121 (development code) (1404)+TX, sulfiram [CCN]+TX, sulfluramid(750)+TX, sulfotep (753)+TX, sulfur (754)+TX, SZI-121 (development code)(757)+TX, tau-fluvalinate (398)+TX, tebufenpyrad (763)+TX, TEPP(1417)+TX, terbam+TX, tetrachlorvinphos (777)+TX, tetradifon (786)+TX,tetranactin (653)+TX, tetrasul (1425)+TX, thiafenox+TX, thiocarboxime(1431)+TX, thiofanox (800)+TX, thiometon (801)+TX, thioquinox (1436)+TX,thuringiensin [CCN]+TX, triamiphos (1441)+TX, triarathene (1443)+TX,triazophos (820)+TX, triazuron+TX, trichlorfon (824)+TX, trifenofos(1455)+TX, trinactin (653)+TX, vamidothion (847)+TX, vaniliprole [CCN]and YI-5302 (compound code)+TX,

an algicide selected from the group of substances consisting ofbethoxazin [CCN]+TX, copper dioctanoate (IUPAC name) (170)+TX, coppersulfate (172)+TX, cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen(232)+TX, endothal (295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX,nabam (566)+TX, quinoclamine (714)+TX, quinonamid (1379)+TX, simazine(730)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltinhydroxide (IUPAC name) (347)+TX,

an anthelmintic selected from the group of substances consisting ofabamectin (1)+TX, crufomate (1011)+TX, doramectin [CCN]+TX, emamectin(291)+TX, emamectin benzoate (291)+TX, eprinomectin [CCN]+TX, ivermectin[CCN]+TX, milbemycin oxime [CCN]+TX, moxidectin [CCN]+TX, piperazine[CCN]+TX, selamectin [CCN]+TX, spinosad (737) and thiophanate (1435)+TX,

an avicide selected from the group of substances consisting ofchloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX,pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX,

a bactericide selected from the group of substances consisting of1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copperdioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name)(169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione(1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde(404)+TX, hydrargaphen [CCN]+TX, kasugamycin (483)+TX, kasugamycinhydrochloride hydrate (483)+TX, nickel bis(dimethyldithiocarbamate)(IUPAC name) (1308)+TX, nitrapyrin (580)+TX, octhilinone (590)+TX,oxolinic acid (606)+TX, oxytetracycline (611)+TX, potassiumhydroxyquinoline sulfate (446)+TX, probenazole (658)+TX, streptomycin(744)+TX, streptomycin sesquisulfate (744)+TX, tecloftalam (766)+TX, andthiomersal [CCN]+TX,

a biological agent selected from the group of substances consisting ofAdoxophyes orana GV (12)+TX, Agrobacterium radiobacter (13)+TX,Amblyseius spp. (19)+TX, Anagrapha falcifera NPV (28)+TX, Anagrus atomus(29)+TX, Aphelinus abdominalis (33)+TX, Aphidius colemani (34)+TX,Aphidoletes aphidimyza (35)+TX, Autographa californica NPV (38)+TX,Bacillus firmus (48)+TX, Bacillus sphaericus Neide (scientific name)(49)+TX, Bacillus thuringiensis Berliner (scientific name) (51)+TX,Bacillus thuringiensis subsp. aizawai (scientific name) (51)+TX,Bacillus thuringiensis subsp. israelensis (scientific name) (51)+TX,Bacillus thuringiensis subsp. japonensis (scientific name) (51)+TX,Bacillus thuringiensis subsp. kurstaki (scientific name) (51)+TX,Bacillus thuringiensis subsp. tenebrionis (scientific name) (51)+TX,Beauveria bassiana (53)+TX, Beauveria brongniartii (54)+TX, Chrysoperlacarnea (151)+TX, Cryptolaemus montrouzieri (178)+TX, Cydia pomonella GV(191)+TX, Dacnusa sibirica (212)+TX, Diglyphus isaea (254)+TX, Encarsiaformosa (scientific name) (293)+TX, Eretmocerus eremicus (300)+TX,Helicoverpa zea NPV (431)+TX, Heterorhabditis bacteriophora and H.megidis (433)+TX, Hippodamia convergens (442)+TX, Leptomastix dactylopii(488)+TX, Macrolophus caliginosus (491)+TX, Mamestra brassicae NPV(494)+TX, Metaphycus helvolus (522)+TX, Metarhizium anisopliae var.acridum (scientific name) (523)+TX, Metarhizium anisopliae var.anisopliae (scientific name) (523)+TX, Neodiprion sertifer NPV and N.lecontei NPV (575)+TX, Orius spp. (596)+TX, Paecilomyces fumosoroseus(613)+TX, Phytoseiulus persimilis (644)+TX, Spodoptera exiguamulticapsid nuclear polyhedrosis virus (scientific name) (741)+TX,Steinernema bibionis (742)+TX, Steinernema carpocapsae (742)+TX,Steinernema feltiae (742)+TX, Steinernema glaseri (742)+TX, Steinernemariobrave (742)+TX, Steinernema riobravis (742)+TX, Steinernemascapterisci (742)+TX, Steinernema spp. (742)+TX, Trichogramma spp.(826)+TX, Typhlodromus occidentalis (844) and Verticillium lecanii(848)+TX,

a soil sterilant selected from the group of substances consisting ofiodomethane (IUPAC name) (542) and methyl bromide (537)+TX,

a chemosterilant selected from the group of substances consisting ofapholate [CCN]+TX, bisazir [CCN]+TX, busulfan [CCN]+TX, diflubenzuron(250)+TX, dimatif [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa[CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid[CCN]+TX, penfluron [CCN]+TX, tepa [CCN]+TX, thiohempa [CCN]+TX,thiotepa [CCN]+TX, tretamine [CCN] and uredepa [CCN]+TX,

an insect pheromone selected from the group of substances consisting of(E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222)+TX,(E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX,(E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX,(E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779)+TX,(Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal(IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name)(437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX,(Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al(IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX,(Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX,(7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283)+TX,(9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780)+TX,(9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781)+TX,14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin [CCN]+TX,brevicomin [CCN]+TX, codlelure [CCN]+TX, codlemone (167)+TX, cuelure(179)+TX, disparlure (277)+TX, dodec-8-en-1-yl acetate (IUPAC name)(286)+TX, dodec-9-en-1-yl acetate (IUPAC name) (287)+TX, dodeca-8+TX,10-dien-1-yl acetate (IUPAC name) (284)+TX, dominicalure [CCN]+TX, ethyl4-methyloctanoate (IUPAC name) (317)+TX, eugenol [CCN]+TX, frontalin[CCN]+TX, gossyplure (420)+TX, grandlure (421)+TX, grandlure I (421)+TX,grandlure II (421)+TX, grandlure III (421)+TX, grandlure IV (421)+TX,hexalure [CCN]+TX, ipsdienol [CCN]+TX, ipsenol [CCN]+TX, japonilure(481)+TX, lineatin [CCN]+TX, litlure [CCN]+TX, looplure [CCN]+TX,medlure [CCN]+TX, megatomoic acid [CCN]+TX, methyl eugenol (540)+TX,muscalure (563)+TX, octadeca-2,13-dien-1-yl acetate (IUPAC name)(588)+TX, octadeca-3,13-dien-1-yl acetate (IUPAC name) (589)+TX,orfralure [CCN]+TX, oryctalure (317)+TX, ostramone [CCN]+TX, siglure[CCN]+TX, sordidin (736)+TX, sulcatol [CCN]+TX, tetradec-11-en-1-ylacetate (IUPAC name) (785)+TX, trimedlure (839)+TX, trimedlure A(839)+TX, trimedlure B, (839)+TX, trimedlure B2 (839)+TX, trimedlure C(839) and trunc-call [CCN]+TX,

an insect repellent selected from the group of substances consisting of2-(octylthio)ethanol (IUPAC name) (591)+TX, butopyronoxyl (933)+TX,butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC name)(1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC name)(1048)+TX, diethyltoluamide [CCN]+TX, dimethyl carbate [CCN]+TX,dimethyl phthalate [CCN]+TX, ethyl hexanediol (1137)+TX, hexamide[CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX,oxamate [CCN] and picaridin [CCN]+TX,

an insecticide selected from the group of substances consisting of1-dichloro-1-nitroethane (IUPAC/Chemical Abstracts name) (1058)+TX,1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056),+TX,1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX,1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX,1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916)+TX,2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name)(1451)+TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate(IUPAC name) (1066)+TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate(IUPAC/Chemical Abstracts name) (1109)+TX, 2-(2-butoxyethoxy)ethylthiocyanate (IUPAC/Chemical Abstracts name) (935)+TX,2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/ChemicalAbstracts name) (1084)+TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name)(986)+TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984)+TX,2-imidazolidone (IUPAC name) (1225)+TX, 2-isovalerylindan-1,3-dione(IUPAC name) (1246)+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate(IUPAC name) (1284)+TX, 2-thiocyanatoethyl laurate (IUPAC name)(1433)+TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917)+TX,3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283)+TX,4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name)(1285)+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPACname) (1085)+TX, abamectin (1)+TX, acephate (2)+TX, acetamiprid (4)+TX,acethion [CCN]+TX, acetoprole [CCN]+TX, acrinathrin (9)+TX,acrylonitrile (IUPAC name) (861)+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, aldrin (864)+TX, allethrin (17)+TX,allosamidin [CCN]+TX, allyxycarb (866)+TX, alpha-cypermethrin (202)+TX,alpha-ecdysone [CCN]+TX, aluminium phosphide (640)+TX, amidithion(870)+TX, amidothioate (872)+TX, aminocarb (873)+TX, amiton (875)+TX,amiton hydrogen oxalate (875)+TX, amitraz (24)+TX, anabasine (877)+TX,athidathion (883)+TX, AVI 382 (compound code)+TX, AZ 60541 (compoundcode)+TX, azadirachtin (41)+TX, azamethiphos (42)+TX, azinphos-ethyl(44)+TX, azinphos-methyl (45)+TX, azothoate (889)+TX, Bacillusthuringiensis delta endotoxins (52)+TX, barium hexafluorosilicate[CCN]+TX, barium polysulfide (IUPAC/Chemical Abstracts name) (892)+TX,barthrin [CCN]+TX, Bayer 22/190 (development code) (893)+TX, Bayer 22408(development code) (894)+TX, bendiocarb (58)+TX, benfuracarb (60)+TX,bensultap (66)+TX, beta-cyfluthrin (194)+TX, beta-cypermethrin (203)+TX,bifenthrin (76)+TX, bioallethrin (78)+TX, bioallethrin S-cyclopentenylisomer (79)+TX, bioethanomethrin [CCN]+TX, biopermethrin (908)+TX,bioresmethrin (80)+TX, bis(2-chloroethyl) ether (IUPAC name) (909)+TX,bistrifluron (83)+TX, borax (86)+TX, brofenvalerate+TX, bromfenvinfos(914)+TX, bromocyclen (918)+TX, bromo-DDT [CCN]+TX, bromophos (920)+TX,bromophos-ethyl (921)+TX, bufencarb (924)+TX, buprofezin (99)+TX,butacarb (926)+TX, butathiofos (927)+TX, butocarboxim (103)+TX, butonate(932)+TX, butoxycarboxim (104)+TX, butylpyridaben+TX, cadusafos(109)+TX, calcium arsenate [CCN]+TX, calcium cyanide (444)+TX, calciumpolysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX, carbanolate(943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbon disulfide(IUPAC/Chemical Abstracts name) (945)+TX, carbon tetrachloride (IUPACname) (946)+TX, carbophenothion (947)+TX, carbosulfan (119)+TX, cartap(123)+TX, cartap hydrochloride (123)+TX, cevadine (725)+TX,chlorbicyclen (960)+TX, chlordane (128)+TX, chlordecone (963)+TX,chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorethoxyfos (129)+TX, chlorfenapyr (130)+TX, chlorfenvinphos(131)+TX, chlorfluazuron (132)+TX, chlormephos (136)+TX, chloroform[CCN]+TX, chloropicrin (141)+TX, chlorphoxim (989)+TX, chlorprazophos(990)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX,chlorthiophos (994)+TX, chromafenozide (150)+TX, cinerin I (696)+TX,cinerin II (696)+TX, cinerins (696)+TX, cis-resmethrin+TX, cismethrin(80)+TX, clocythrin+TX, cloethocarb (999)+TX, closantel [CCN]+TX,clothianidin (165)+TX, copper acetoarsenite [CCN]+TX, copper arsenate[CCN]+TX, copper oleate [CCN]+TX, coumaphos (174)+TX, coumithoate(1006)+TX, crotamiton [CCN]+TX, crotoxyphos (1010)+TX, crufomate(1011)+TX, cryolite (177)+TX, CS 708 (development code) (1012)+TX,cyanofenphos (1019)+TX, cyanophos (184)+TX, cyanthoate (1020)+TX,cyclethrin [CCN]+TX, cycloprothrin (188)+TX, cyfluthrin (193)+TX,cyhalothrin (196)+TX, cypermethrin (201)+TX, cyphenothrin (206)+TX,cyromazine (209)+TX, cythioate [CCN]+TX, d-limonene [CCN]+TX,d-tetramethrin (788)+TX, DAEP (1031)+TX, dazomet (216)+TX, DDT (219)+TX,decarbofuran (1034)+TX, deltamethrin (223)+TX, demephion (1037)+TX,demephion-O (1037)+TX, demephion-S (1037)+TX, demeton (1038)+TX,demeton-methyl (224)+TX, demeton-O (1038)+TX, demeton-O-methyl (224)+TX,demeton-S (1038)+TX, demeton-S-methyl (224)+TX, demeton-S-methylsulphon(1039)+TX, diafenthiuron (226)+TX, dialifos (1042)+TX, diamidafos(1044)+TX, diazinon (227)+TX, dicapthon (1050)+TX, dichlofenthion(1051)+TX, dichlorvos (236)+TX, dicliphos+TX, dicresyl [CCN]+TX,dicrotophos (243)+TX, dicyclanil (244)+TX, dieldrin (1070)+TX, diethyl5-methylpyrazol-3-yl phosphate (IUPAC name) (1076)+TX, diflubenzuron(250)+TX, dilor [CCN]+TX, dimefluthrin [CCN]+TX, dimefox (1081)+TX,dimetan (1085)+TX, dimethoate (262)+TX, dimethrin (1083)+TX,dimethylvinphos (265)+TX, dimetilan (1086)+TX, dinex (1089)+TX,dinex-diclexine (1089)+TX, dinoprop (1093)+TX, dinosam (1094)+TX,dinoseb (1095)+TX, dinotefuran (271)+TX, diofenolan (1099)+TX,dioxabenzofos (1100)+TX, dioxacarb (1101)+TX, dioxathion (1102)+TX,disulfoton (278)+TX, dithicrofos (1108)+TX, DNOC (282)+TX, doramectin[CCN]+TX, DSP (1115)+TX, ecdysterone [CCN]+TX, EI 1642 (developmentcode) (1118)+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, EMPC(1120)+TX, empenthrin (292)+TX, endosulfan (294)+TX, endothion(1121)+TX, endrin (1122)+TX, EPBP (1123)+TX, EPN (297)+TX, epofenonane(1124)+TX, eprinomectin [CCN]+TX, esfenvalerate (302)+TX, etaphos[CCN]+TX, ethiofencarb (308)+TX, ethion (309)+TX, ethiprole (310)+TX,ethoate-methyl (1134)+TX, ethoprophos (312)+TX, ethyl formate (IUPACname) [CCN]+TX, ethyl-DDD (1056)+TX, ethylene dibromide (316)+TX,ethylene dichloride (chemical name) (1136)+TX, ethylene oxide [CCN]+TX,etofenprox (319)+TX, etrimfos (1142)+TX, EXD (1143)+TX, famphur(323)+TX, fenamiphos (326)+TX, fenazaflor (1147)+TX, fenchlorphos(1148)+TX, fenethacarb (1149)+TX, fenfluthrin (1150)+TX, fenitrothion(335)+TX, fenobucarb (336)+TX, fenoxacrim (1153)+TX, fenoxycarb(340)+TX, fenpirithrin (1155)+TX, fenpropathrin (342)+TX, fenpyrad+TX,fensulfothion (1158)+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX,fenvalerate (349)+TX, fipronil (354)+TX, flonicamid (358)+TX,flubendiamide (CAS. Reg. No.: 272451-65-7)+TX, flucofuron (1168)+TX,flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX,flufenerim [CCN]+TX, flufenoxuron (370)+TX, flufenprox (1171)+TX,flumethrin (372)+TX, fluvalinate (1184)+TX, FMC 1137 (development code)(1185)+TX, fonofos (1191)+TX, formetanate (405)+TX, formetanatehydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX,fosmethilan (1194)+TX, fospirate (1195)+TX, fosthiazate (408)+TX,fosthietan (1196)+TX, furathiocarb (412)+TX, furethrin (1200)+TX,gamma-cyhalothrin (197)+TX, gamma-HCH (430)+TX, guazatine (422)+TX,guazatine acetates (422)+TX, GY-81 (development code) (423)+TX,halfenprox (424)+TX, halofenozide (425)+TX, HCH (430)+TX, HEOD(1070)+TX, heptachlor (1211)+TX, heptenophos (432)+TX, heterophos[CCN]+TX, hexaflumuron (439)+TX, HHDN (864)+TX, hydramethylnon (443)+TX,hydrogen cyanide (444)+TX, hydroprene (445)+TX, hyquincarb (1223)+TX,imidacloprid (458)+TX, imiprothrin (460)+TX, indoxacarb (465)+TX,iodomethane (IUPAC name) (542)+TX, IPSP (1229)+TX, isazofos (1231)+TX,isobenzan (1232)+TX, isocarbophos (473)+TX, isodrin (1235)+TX,isofenphos (1236)+TX, isolane (1237)+TX, isoprocarb (472)+TX, isopropylO-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX,isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion (480)+TX,ivermectin [CCN]+TX, jasmolin I (696)+TX, jasmolin II (696)+TX,jodfenphos (1248)+TX, juvenile hormone I [CCN]+TX, juvenile hormone II[CCN]+TX, juvenile hormone III [CCN]+TX, kelevan (1249)+TX, kinoprene(484)+TX, lambda-cyhalothrin (198)+TX, lead arsenate [CCN]+TX,lepimectin (CCN)+TX, leptophos (1250)+TX, lindane (430)+TX, lirimfos(1251)+TX, lufenuron (490)+TX, lythidathion (1253)+TX, m-cumenylmethylcarbamate (IUPAC name) (1014)+TX, magnesium phosphide (IUPAC name)(640)+TX, malathion (492)+TX, malonoben (1254)+TX, mazidox (1255)+TX,mecarbam (502)+TX, mecarphon (1258)+TX, menazon (1260)+TX, mephosfolan(1261)+TX, mercurous chloride (513)+TX, mesulfenfos (1263)+TX,metaflumizone (CCN)+TX, metam (519)+TX, metam-potassium (519)+TX,metam-sodium (519)+TX, methacrifos (1266)+TX, methamidophos (527)+TX,methanesulfonyl fluoride (IUPAC/Chemical Abstracts name) (1268)+TX,methidathion (529)+TX, methiocarb (530)+TX, methocrotophos (1273)+TX,methomyl (531)+TX, methoprene (532)+TX, methoquin-butyl (1276)+TX,methothrin (533)+TX, methoxychlor (534)+TX, methoxyfenozide (535)+TX,methyl bromide (537)+TX, methyl isothiocyanate (543)+TX,methylchloroform [CCN]+TX, methylene chloride [CCN]+TX, metofluthrin[CCN]+TX, metolcarb (550)+TX, metoxadiazone (1288)+TX, mevinphos(556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime[CCN]+TX, mipafox (1293)+TX, mirex (1294)+TX, monocrotophos (561)+TX,morphothion (1300)+TX, moxidectin [CCN]+TX, naftalofos [CCN]+TX, naled(567)+TX, naphthalene (IUPAC/Chemical Abstracts name) (1303)+TX, NC-170(development code) (1306)+TX, NC-184 (compound code)+TX, nicotine(578)+TX, nicotine sulfate (578)+TX, nifluridide (1309)+TX, nitenpyram(579)+TX, nithiazine (1311)+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250(compound code)+TX, nornicotine (traditional name) (1319)+TX, novaluron(585)+TX, noviflumuron (586)+TX, O-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate (IUPAC name) (1057)+TX, O,O-diethylO-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name)(1074)+TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphorothioate (IUPAC name) (1075)+TX, O,O,O′,O′-tetrapropyldithiopyrophosphate (IUPAC name) (1424)+TX, oleic acid (IUPAC name)(593)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydemeton-methyl(609)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp′-DDT(219)+TX, para-dichlorobenzene [CCN]+TX, parathion (615)+TX,parathion-methyl (616)+TX, penfluron [CCN]+TX, pentachlorophenol(623)+TX, pentachlorophenyl laurate (IUPAC name) (623)+TX, permethrin(626)+TX, petroleum oils (628)+TX, PH 60-38 (development code)(1328)+TX, phenkapton (1330)+TX, phenothrin (630)+TX, phenthoate(631)+TX, phorate (636)+TX, phosalone (637)+TX, phosfolan (1338)+TX,phosmet (638)+TX, phosnichlor (1339)+TX, phosphamidon (639)+TX,phosphine (IUPAC name) (640)+TX, phoxim (642)+TX, phoxim-methyl(1340)+TX, pirimetaphos (1344)+TX, pirimicarb (651)+TX, pirimiphos-ethyl(1345)+TX, pirimiphos-methyl (652)+TX, polychlorodicyclopentadieneisomers (IUPAC name) (1346)+TX, polychloroterpenes (traditional name)(1347)+TX, potassium arsenite [CCN]+TX, potassium thiocyanate [CCN]+TX,prallethrin (655)+TX, precocene I [CCN]+TX, precocene II [CCN]+TX,precocene III [CCN]+TX, primidophos (1349)+TX, profenofos (662)+TX,profluthrin [CCN]+TX, promacyl (1354)+TX, promecarb (1355)+TX, propaphos(1356)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion(1360)+TX, prothiofos (686)+TX, prothoate (1362)+TX, protrifenbute[CCN]+TX, pymetrozine (688)+TX, pyraclofos (689)+TX, pyrazophos(693)+TX, pyresmethrin (1367)+TX, pyrethrin I (696)+TX, pyrethrin II(696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridalyl (700)+TX,pyridaphenthion (701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX,pyriproxyfen (708)+TX, quassia [CCN]+TX, quinalphos (711)+TX,quinalphos-methyl (1376)+TX, quinothion (1380)+TX, quintiofos (1381)+TX,R-1492 (development code) (1382)+TX, rafoxanide [CCN]+TX, resmethrin(719)+TX, rotenone (722)+TX, RU 15525 (development code) (723)+TX, RU25475 (development code) (1386)+TX, ryania (1387)+TX, ryanodine(traditional name) (1387)+TX, sabadilla (725)+TX, schradan (1389)+TX,sebufos+TX, selamectin [CCN]+TX, SI-0009 (compound code)+TX, SI-0205(compound code)+TX, SI-0404 (compound code)+TX, SI-0405 (compoundcode)+TX, silafluofen (728)+TX, SN 72129 (development code) (1397)+TX,sodium arsenite [CCN]+TX, sodium cyanide (444)+TX, sodium fluoride(IUPAC/Chemical Abstracts name) (1399)+TX, sodium hexafluorosilicate(1400)+TX, sodium pentachlorophenoxide (623)+TX, sodium selenate (IUPACname) (1401)+TX, sodium thiocyanate [CCN]+TX, sophamide (1402)+TX,spinosad (737)+TX, spiromesifen (739)+TX, spirotetrmat (CCN)+TX,sulcofuron (746)+TX, sulcofuron-sodium (746)+TX, sulfluramid (750)+TX,sulfotep (753)+TX, sulfuryl fluoride (756)+TX, sulprofos (1408)+TX, taroils (758)+TX, tau-fluvalinate (398)+TX, tazimcarb (1412)+TX, TDE(1414)+TX, tebufenozide (762)+TX, tebufenpyrad (763)+TX, tebupirimfos(764)+TX, teflubenzuron (768)+TX, tefluthrin (769)+TX, temephos(770)+TX, TEPP (1417)+TX, terallethrin (1418)+TX, terbam+TX, terbufos(773)+TX, tetrachloroethane [CCN]+TX, tetrachlorvinphos (777)+TX,tetramethrin (787)+TX, theta-cypermethrin (204)+TX, thiacloprid(791)+TX, thiafenox+TX, thiamethoxam (792)+TX, thicrofos (1428)+TX,thiocarboxime (1431)+TX, thiocyclam (798)+TX, thiocyclam hydrogenoxalate (798)+TX, thiodicarb (799)+TX, thiofanox (800)+TX, thiometon(801)+TX, thionazin (1434)+TX, thiosultap (803)+TX, thiosultap-sodium(803)+TX, thuringiensin [CCN]+TX, tolfenpyrad (809)+TX, tralomethrin(812)+TX, transfluthrin (813)+TX, transpermethrin (1440)+TX, triamiphos(1441)+TX, triazamate (818)+TX, triazophos (820)+TX, triazuron+TX,trichlorfon (824)+TX, trichlormetaphos-3 [CCN]+TX, trichloronat(1452)+TX, trifenofos (1455)+TX, triflumuron (835)+TX, trimethacarb(840)+TX, triprene (1459)+TX, vamidothion (847)+TX, vaniliprole[CCN]+TX, veratridine (725)+TX, veratrine (725)+TX, XMC (853)+TX,xylylcarb (854)+TX, YI-5302 (compound code)+TX, zeta-cypermethrin(205)+TX, zetamethrin+TX, zinc phosphide (640)+TX, zolaprofos (1469) andZXI 8901 (development code) (858)+TX, cyantraniliprole [736994-63-19+TX,chlorantraniliprole [500008-45-7]+TX, cyenopyrafen [560121-52-0]+TX,cyflumetofen [400882-07-7]+TX, pyrifluquinazon [337458-27-2]+TX,spinetoram [187166-40-1+187166-15-0]+TX, spirotetramat [203313-25-1]+TX,sulfoxaflor [946578-00-3]+TX, flufiprole [704886-18-0]+TX, meperfluthrin[915288-13-0]+TX, tetramethylfluthrin [84937-88-2]+TX, triflumezopyrim(disclosed in WO 2012/092115)+TX, fluxametamide (WO 2007/026965)+TX,epsilon-metofluthrin [240494-71-7]+TX, epsilon-momfluorothrin[1065124-65-3]+TX, fluazaindolizine [1254304-22-7]+TX, chloroprallethrin[399572-87-3]+TX, fluxametamide [928783-29-3]+TX, cyhalodiamide[1262605-53-7]+TX, tioxazafen [330459-31-9]+TX, broflanilide[1207727-04-5]+TX, flufiprole [704886-18-0]+TX, cyclaniliprole[1031756-98-5]+TX, tetraniliprole [1229654-66-3]+TX, guadipyr (describedin WO2010/060231)+TX, cycloxaprid (described in WO2005/077934)+TX,

a molluscicide selected from the group of substances consisting ofbis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX,calcium arsenate [CCN]+TX, cloethocarb (999)+TX, copper acetoarsenite[CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, ferric phosphate(IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX,niclosamide (576)+TX, niclosamide-olamine (576)+TX, pentachlorophenol(623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX,thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX,trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) andtriphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole[394730-71-3]+TX,

a nematicide selected from the group of substances consisting ofAKD-3088 (compound code)+TX, 1,2-dibromo-3-chloropropane (IUPAC/ChemicalAbstracts name) (1045)+TX, 1,2-dichloropropane (IUPAC/Chemical Abstractsname) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPACname) (1063)+TX, 1,3-dichloropropene (233)+TX,3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstractsname) (1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name)(980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPACname) (1286)+TX, 6-isopentenylaminopurine (210)+TX, abamectin (1)+TX,acetoprole [CCN]+TX, alanycarb (15)+TX, aldicarb (16)+TX, aldoxycarb(863)+TX, AZ 60541 (compound code)+TX, benclothiaz [CCN]+TX, benomyl(62)+TX, butylpyridaben+TX, cadusafos (109)+TX, carbofuran (118)+TX,carbon disulfide (945)+TX, carbosulfan (119)+TX, chloropicrin (141)+TX,chlorpyrifos (145)+TX, cloethocarb (999)+TX, cytokinins (210)+TX,dazomet (216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos (1044)+TX,dichlofenthion (1051)+TX, dicliphos+TX, dimethoate (262)+TX, doramectin[CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin[CCN]+TX, ethoprophos (312)+TX, ethylene dibromide (316)+TX, fenamiphos(326)+TX, fenpyrad+TX, fensulfothion (1158)+TX, fosthiazate (408)+TX,fosthietan (1196)+TX, furfural [CCN]+TX, GY-81 (development code)(423)+TX, heterophos [CCN]+TX, iodomethane (IUPAC name) (542)+TX,isamidofos (1230)+TX, isazofos (1231)+TX, ivermectin [CCN]+TX, kinetin(210)+TX, mecarphon (1258)+TX, metam (519)+TX, metam-potassium (519)+TX,metam-sodium (519)+TX, methyl bromide (537)+TX, methyl isothiocyanate(543)+TX, milbemycin oxime [CCN]+TX, moxidectin [CCN]+TX, Myrotheciumverrucaria composition (565)+TX, NC-184 (compound code)+TX, oxamyl(602)+TX, phorate (636)+TX, phosphamidon (639)+TX, phosphocarb [CCN]+TX,sebufos+TX, selamectin [CCN]+TX, spinosad (737)+TX, terbam+TX, terbufos(773)+TX, tetrachlorothiophene (IUPAC/Chemical Abstracts name)(1422)+TX, thiafenox+TX, thionazin (1434)+TX, triazophos (820)+TX,triazuron+TX, xylenols [CCN]+TX, YI-5302 (compound code) and zeatin(210)+TX, fluensulfone [318290-98-1]+TX,

a nitrification inhibitor selected from the group of substancesconsisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,

a plant activator selected from the group of substances consisting ofacibenzolar (6)+TX, acibenzolar-S-methyl (6)+TX, probenazole (658) andReynoutria sachalinensis extract (720)+TX,

a rodenticide selected from the group of substances consisting of2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX, antu(880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX,bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX,bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX,chlorophacinone (140)+TX, cholecalciferol (850)+TX, coumachlor(1004)+TX, coumafuryl (1005)+TX, coumatetralyl (175)+TX, crimidine(1009)+TX, difenacoum (246)+TX, difethialone (249)+TX, diphacinone(273)+TX, ergocalciferol (301)+TX, flocoumafen (357)+TX, fluoroacetamide(379)+TX, flupropadine (1183)+TX, flupropadine hydrochloride (1183)+TX,gamma-HCH (430)+TX, HCH (430)+TX, hydrogen cyanide (444)+TX, iodomethane(IUPAC name) (542)+TX, lindane (430)+TX, magnesium phosphide (IUPACname) (640)+TX, methyl bromide (537)+TX, norbormide (1318)+TX,phosacetim (1336)+TX, phosphine (IUPAC name) (640)+TX, phosphorus[CCN]+TX, pindone (1341)+TX, potassium arsenite [CCN]+TX, pyrinuron(1371)+TX, scilliroside (1390)+TX, sodium arsenite [CCN]+TX, sodiumcyanide (444)+TX, sodium fluoro-acetate (735)+TX, strychnine (745)+TX,thallium sulfate [CCN]+TX, warfarin (851) and zinc phosphide (640)+TX,

a synergist selected from the group of substances consisting of2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934)+TX,5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX,farnesol with nerolidol (324)+TX, MB-599 (development code) (498)+TX,MGK 264 (development code) (296)+TX, piperonyl butoxide (649)+TX,piprotal (1343)+TX, propyl isomer (1358)+TX, S421 (development code)(724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide (1406)+TX,

an animal repellent selected from the group of substances consisting ofanthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX,copper oxychloride (171)+TX, diazinon (227)+TX, dicyclopentadiene(chemical name) (1069)+TX, guazatine (422)+TX, guazatine acetates(422)+TX, methiocarb (530)+TX, pyridin-4-amine (IUPAC name) (23)+TX,thiram (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram(856)+TX,

a virucide selected from the group of substances consisting of imanin[CCN] and ribavirin [CCN]+TX,

a wound protectant selected from the group of substances consisting ofmercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl(802)+TX,

and biologically active compounds selected from the group consisting ofazaconazole (60207-31-0]+TX, bitertanol [70585-36-3]+TX, bromuconazole[116255-48-2]+TX, cyproconazole [94361-06-5]+TX, difenoconazole[119446-68-3]+TX, diniconazole [83657-24-3]+TX, epoxiconazole[106325-08-0]+TX, fenbuconazole [114369-43-6]+TX, fluquinconazole[136426-54-5]+TX, flusilazole [85509-19-9]+TX, flutriafol[76674-21-0]+TX, hexaconazole [79983-71-4]+TX, imazalil [35554-44-0]+TX,imibenconazole [86598-92-7]+TX, ipconazole [125225-28-7]+TX, metconazole[125116-23-6]+TX, myclobutanil [88671-89-0]+TX, pefurazoate[101903-30-4]+TX, penconazole [66246-88-6]+TX, prothioconazole[178928-70-6]+TX, pyrifenox [88283-41-4]+TX, prochloraz [67747-09-5]+TX,propiconazole [60207-90-1]+TX, simeconazole [149508-90-7]+TX,tebuconazole [107534-96-3]+TX, tetraconazole [112281-77-3]+TX,triadimefon [43121-43-3]+TX, triadimenol [55219-65-3]+TX, triflumizole[99387-89-0]+TX, triticonazole [131983-72-7]+TX, ancymidol[12771-68-5]+TX, fenarimol [60168-88-9]+TX, nuarimol [63284-71-9]+TX,bupirimate [41483-43-6]+TX, dimethirimol [5221-53-4]+TX, ethirimol[23947-60-6]+TX, dodemorph [1593-77-7]+TX, fenpropidine [67306-00-7]+TX,fenpropimorph [67564-91-4]+TX, spiroxamine [118134-30-8]+TX, tridemorph[81412-43-3]+TX, cyprodinil [121552-61-2]+TX, mepanipyrim[110235-47-7]+TX, pyrimethanil [53112-28-0]+TX, fenpiclonil[74738-17-3]+TX, fludioxonil [131341-86-1]+TX, benalaxyl[71626-11-4]+TX, furalaxyl [57646-30-7]+TX, metalaxyl [57837-19-1]+TX,R-metalaxyl [70630-17-0]+TX, ofurace [58810-48-3]+TX, oxadixyl[77732-09-3]+TX, benomyl [17804-35-2]+TX, carbendazim [10605-21-7]+TX,debacarb [62732-91-6]+TX, fuberidazole [3878-19-1]+TX, thiabendazole[148-79-8]+TX, chlozolinate [84332-86-5]+TX, dichlozoline[24201-58-9]+TX, iprodione [36734-19-7]+TX, myclozoline [54864-61-8]+TX,procymidone [32809-16-8]+TX, vinclozoline [50471-44-8]+TX, boscalid[188425-85-6]+TX, carboxin [5234-68-4]+TX, fenfuram [24691-80-3]+TX,flutolanil [66332-96-5]+TX, mepronil [55814-41-0]+TX, oxycarboxin[5259-88-1]+TX, penthiopyrad [183675-82-3]+TX, thifluzamide[130000-40-7]+TX, guazatine [108173-90-6]+TX, dodine [2439-10-3][112-65-2] (free base)+TX, iminoctadine [13516-27-3]+TX, azoxystrobin[131860-33-8]+TX, dimoxystrobin [149961-52-4]+TX, enestroburin {Proc.BCPC, Int. Congr., Glasgow, 2003, 1, 93}+TX, fluoxastrobin[361377-29-9]+TX, kresoxim-methyl [143390-89-0]+TX, metominostrobin[133408-50-1]+TX, trifloxystrobin [141517-21-7]+TX, orysastrobin[248593-16-0]+TX, picoxystrobin [117428-22-5]+TX, pyraclostrobin[175013-18-0]+TX, ferbam [14484-64-1]+TX, mancozeb [8018-01-7]+TX, maneb[12427-38-2]+TX, metiram [9006-42-2]+TX, propineb [12071-83-9]+TX,thiram [137-26-8]+TX, zineb [12122-67-7]+TX, ziram [137-30-4]+TX,captafol [2425-06-1]+TX, captan [133-06-2]+TX, dichlofluanid[1085-98-9]+TX, fluoroimide [41205-21-4]+TX, folpet [133-07-3]+TX,tolylfluanid [731-27-1]+TX, bordeaux mixture [8011-63-0]+TX,copperhydroxid [20427-59-2]+TX, copperoxychlorid [1332-40-7]+TX,coppersulfat [7758-98-7]+TX, copperoxid [1317-39-1]+TX, mancopper[53988-93-5]+TX, oxine-copper [10380-28-6]+TX, dinocap [131-72-6]+TX,nitrothal-isopropyl [10552-74-6]+TX, edifenphos [17109-49-8]+TX,iprobenphos [26087-47-8]+TX, isoprothiolane [50512-35-1]+TX, phosdiphen[36519-00-3]+TX, pyrazophos [13457-18-6]+TX, tolclofos-methyl[57018-04-9]+TX, acibenzolar-S-methyl [135158-54-2]+TX, anilazine[101-05-3]+TX, benthiavalicarb [413615-35-7]+TX, blasticidin-S[2079-00-7]+TX, chinomethionat [2439-01-2]+TX, chloroneb [2675-77-6]+TX,chlorothalonil [1897-45-6]+TX, cyflufenamid [180409-60-3]+TX, cymoxanil[57966-95-7]+TX, dichlone [117-80-6]+TX, diclocymet [139920-32-4]+TX,diclomezine [62865-36-5]+TX, dicloran [99-30-9]+TX, diethofencarb[87130-20-9]+TX, dimethomorph [110488-70-5]+TX, SYP-LI90 (Flumorph)[211867-47-9]+TX, dithianon [3347-22-6]+TX, ethaboxam [162650-77-3]+TX,etridiazole [2593-15-9]+TX, famoxadone [131807-57-3]+TX, fenamidone[161326-34-7]+TX, fenoxanil [115852-48-7]+TX, fentin [668-34-8]+TX,ferimzone [89269-64-7]+TX, fluazinam [79622-59-6]+TX, fluopicolide[239110-15-7]+TX, flusulfamide [106917-52-6]+TX, fenhexamid[126833-17-8]+TX, fosetyl-aluminium [39148-24-8]+TX, hymexazol[10004-44-1]+TX, iprovalicarb [140923-17-7]+TX, IKF-916 (Cyazofamid)[120116-88-3]+TX, kasugamycin [6980-18-3]+TX, methasulfocarb[66952-49-6]+TX, metrafenone [220899-03-6]+TX, pencycuron[66063-05-6]+TX, phthalide [27355-22-2]+TX, polyoxins [11113-80-7]+TX,probenazole [27605-76-1]+TX, propamocarb [25606-41-1]+TX, proquinazid[189278-12-4]+TX, pyroquilon [57369-32-1]+TX, quinoxyfen[124495-18-7]+TX, quintozene [82-68-8]+TX, sulfur [7704-34-9]+TX,tiadinil [223580-51-6]+TX, triazoxide [72459-58-6]+TX, tricyclazole[41814-78-2]+TX, triforine [26644-46-2]+TX, validamycin [37248-47-8]+TX,zoxamide (RH7281) [156052-68-5]+TX, mandipropamid [374726-62-2]+TX,isopyrazam [881685-58-1]+TX, sedaxane [874967-67-6]+TX,3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide(dislosed in WO 2007/048556)+TX,3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(3′,4′,5′-trifluoro-biphenyl-2-yl)-amide (disclosed in WO2006/087343)+TX,[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11Hnaphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate[915972-17-7]+TX and1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide[926914-55-8]+TX; and

microbials including: Acinetobacter iwoffii+TX, Acremoniumalternatum+TX+TX, Acremonium cephalosporium+TX+TX, Acremoniumdiospyri+TX, Acremonium obclavatum+TX, Adoxophyes orana granulovirus(AdoxGV) (Capex®)+TX, Agrobacterium radiobacter strain K84(Galltrol-A®)+TX, Alternaria alternate+TX, Alternaria cassia+TX,Alternaria destruens (Smolder®)+TX, Ampelomyces quisqualis (AQ10®)+TX,Aspergillus flavus AF36 (AF36®)+TX, Aspergillus flavus NRRL 21882(Aflaguard®)+TX, Aspergillus spp.+TX, Aureobasidium pullulans+TX,Azospirillum+TX, (MicroAZ®+TX, TAZO B®)+TX, Azotobacter+TX, Azotobacterchroocuccum (Azotomeal®)+TX, Azotobacter cysts (Bionatural BloomingBlossoms®)+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX,Bacillus chitinosporus strain CM-1+TX, Bacillus chitinosporus strainAQ746+TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®)+TX,Bacillus licheniformis strain 3086 (EcoGuard®+TX, Green Releaf®)+TX,Bacillus circulans+TX, Bacillus firmus (BioSafe®+TX, BioNem-WP®+TX,VOTiVO®)+TX, Bacillus firmus strain I-1582+TX, Bacillus macerans+TX,Bacillus marismortui+TX, Bacillus megaterium+TX, Bacillus mycoidesstrain AQ726+TX, Bacillus papillae (Milky Spore Powder®)+TX, Bacilluspumilus spp.+TX, Bacillus pumilus strain GB34 (Yield Shield®)+TX,Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808(Sonata®+TX, Ballad Plus®)+TX, Bacillus spahericus (VectoLex®)+TX,Bacillus spp.+TX, Bacillus spp. strain AQ175+TX, Bacillus spp. strainAQ177+TX, Bacillus spp. strain AQ178+TX, Bacillus subtilis strain QST713 (CEASE®+TX, Serenade®+TX, Rhapsody®)+TX, Bacillus subtilis strainQST 714 (JAZZ®)+TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilisstrain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilisstrain QST3004+TX, Bacillus subtilis var. amyloliquefaciens strain FZB24(Taegro®+TX, Rhizopro®)+TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillusthuringiensis Cry1Ab+TX, Bacillus thuringiensis aizawai GC 91(Agree®)+TX, Bacillus thuringiensis israelensis (BMP123®+TX,Aquabac®+TX, VectoBac®)+TX, Bacillus thuringiensis kurstaki(Javelin®+TX, Deliver®+TX, CryMax®+TX, Bonide®+TX, Scutella WP®+TX,Turilav WP®+TX, Astuto®+TX, Dipel WP®+TX, Biobit®+TX, Foray®)+TX,Bacillus thuringiensis kurstaki BMP 123 (Baritone®)+TX, Bacillusthuringiensis kurstaki HD-1 (Bioprotec-CAF/3P®)+TX, Bacillusthuringiensis strain BD#32+TX, Bacillus thuringiensis strain AQ52+TX,Bacillus thuringiensis var. aizawai (XenTari®+TX, DiPel®)+TX, bacteriaspp. (GROWMEND®+TX, GROWSWEET®+TX, Shootup®)+TX, bacteriophage ofClavipacter michiganensis (AgriPhage®)+TX, Bakflor®+TX, Beauveriabassiana (Beaugenic®+TX, Brocaril WP®)+TX, Beauveria bassiana GHA(Mycotrol ES®+TX, Mycotrol O®+TX, BotaniGuard®)+TX, Beauveriabrongniartii (Engerlingspilz®+TX, Schweizer Beauveria®+TX,Melocont®)+TX, Beauveria spp.+TX, Botrytis cineria+TX, Bradyrhizobiumjaponicum (TerraMax®)+TX, Brevibacillus brevis+TX, Bacillusthuringiensis tenebrionis (Novodor®)+TX, BtBooster+TX, Burkholderiacepacia (Deny®+TX, Intercept®+TX, Blue Circle®)+TX, Burkholderiagladii+TX, Burkholderia gladioli+TX, Burkholderia spp.+TX, Canadianthistle fungus (CBH Canadian Bioherbicide®)+TX, Candida butyri+TX,Candida famata+TX, Candida fructus+TX, Candida glabrata+TX, Candidaguilliermondii+TX, Candida melibiosica+TX, Candida oleophila strainO+TX, Candida parapsilosis+TX, Candida pelliculosa+TX, Candidapulcherrima+TX, Candida reukaufii+TX, Candida saitoana (Bio-Coat®+TX,Biocure®)+TX, Candida sake+TX, Candida spp.+TX, Candida tenius+TX,Cedecea dravisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes(Nova-Cide®)+TX, Chaetomium globosum (Nova-Cide®)+TX, Chromobacteriumsubtsugae strain PRAA4-1T (Grandevo®)+TX, Cladosporiumcladosporioides+TX, Cladosporium oxysporum+TX, Cladosporiumchlorocephalum+TX, Cladosporium spp.+TX, Cladosporium tenuissimum+TX,Clonostachys rosea (EndoFine®)+TX, Colletotrichum acutatum+TX,Coniothyrium minitans (Cotans WG®)+TX, Coniothyrium spp.+TX,Cryptococcus albidus (YIELDPLUS®)+TX, Cryptococcus humicola+TX,Cryptococcus infirmo-miniatus+TX, Cryptococcus laurentii+TX,Cryptophlebia leucotreta granulovirus (Cryptex®)+TX, Cupriaviduscampinensis+TX, Cydia pomonella granulovirus (CYD-X®)+TX, Cydiapomonella granulovirus (Madex®+TX, Madex Plus®+TX, MadexMax/Carpovirusine®)+TX, Cylindrobasidium laeve (Stumpout®)+TX,Cylindrocladium+TX, Debaryomyces hansenii+TX, Drechslerahawaiinensis+TX, Enterobacter cloacae+TX, Enterobacteriaceae+TX,Entomophtora virulenta (Vektor®)+TX, Epicoccum nigrum+TX, Epicoccumpurpurascens+TX, Epicoccum spp.+TX, Filobasidium floriforme+TX, Fusariumacuminatum+TX, Fusarium chlamydosporum+TX, Fusarium oxysporum(Fusaclean®/Biofox C®)+TX, Fusarium proliferatum+TX, Fusarium spp.+TX,Galactomyces geotrichum+TX, Gliocladium catenulatum (Primastop®+TX,Prestop®)+TX, Gliocladium roseum+TX, Gliocladium spp. (SoilGard®)+TX,Gliocladium virens (Soilgard®)+TX, Granulovirus (Granupom®)+TX,Halobacillus halophilus+TX, Halobacillus litoralis+TX, Halobacillustrueperi+TX, Halomonas spp.+TX, Halomonas subglaciescola+TX, Halovibriovariabilis+TX, Hanseniaspora uvarum+TX, Helicoverpa armigeranucleopolyhedrovirus (Helicovex®)+TX, Helicoverpa zea nuclearpolyhedrosis virus (Gemstar®)+TX, Isoflavone-formononetin(Myconate®)+TX, Kloeckera apiculata+TX, Kloeckera spp.+TX, Lagenidiumgiganteum (Laginex®)+TX, Lecanicillium longisporum (Vertiblast®)+TX,Lecanicillium muscarium (Vertikil®)+TX, Lymantria disparnucleopolyhedrosis virus (Disparvirus®)+TX, Marinococcus halophilus+TX,Meira geulakonigii+TX, Metarhizium anisopliae (Met52®)+TX, Metarhiziumanisopliae (Destruxin WP®)+TX, Metschnikowia fruticola (Shemer®)+TX,Metschnikowia pulcherrima+TX, Microdochium dimerum (Antibot®)+TX,Micromonospora coerulea+TX, Microsphaeropsis ochracea+TX, Muscodor albus620 (Muscudor®)+TX, Muscodor roseus strain A3-5+TX, Mycorrhizae spp.(AMykor®+TX, Root Maximizer®)+TX, Myrothecium verrucaria strainAARC-0255 (DiTera®)+TX, BROS PLUS®+TX, Ophiostoma piliferum strain D97(Sylvanex®)+TX, Paecilomyces farinosus+TX, Paecilomyces fumosoroseus(PFR-97®+TX, PreFeRal®)+TX, Paecilomyces linacinus (Biostat WP®)+TX,Paecilomyces lilacinus strain 251 (MeloCon WG®)+TX, Paenibacffiuspolymyxa+TX, Pantoea agglomerans (BlightBan C9-1®)+TX, Pantoea spp.+TX,Pasteuria spp. (Econem®)+TX, Pasteuria nishizawae+TX, Penicilliumaurantiogriseum+TX, Penicillium billai (Jumpstart®+TX, TagTeam®)+TX,Penicillium brevicompactum+TX, Penicillium frequentans+TX, Penicilliumgriseofulvum+TX, Penicillium purpurogenum+TX, Penicillium spp.+TX,Penicillium viridicatum+TX, Phlebiopsis gigantean (Rotstop®)+TX,phosphate solubilizing bacteria (Phosphomeal®)+TX, Phytophthoracryptogea+TX, Phytophthora palmivora (Devine®)+TX, Pichia anomala+TX,Pichia guilermondii+TX, Pichia membranaefaciens+TX, Pichia onychis+TX,Pichia stipites+TX, Pseudomonas aeruginosa+TX, Pseudomonas aureofasciens(Spot-Less Biofungicide®)+TX, Pseudomonas cepacia+TX, Pseudomonaschlororaphis (AtEze®)+TX, Pseudomonas corrugate+TX, Pseudomonasfluorescens strain A506 (BlightBan A506®)+TX, Pseudomonas putida+TX,Pseudomonas reactans+TX, Pseudomonas spp.+TX, Pseudomonas syringae(Bio-Save®)+TX, Pseudomonas viridiflava+TX, Pseudomons fluorescens(Zequanox®)+TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®)+TX,Puccinia canaliculata+TX, Puccinia thlaspeos (Wood Warrior®)+TX, Pythiumparoecandrum+TX, Pythium oligandrum (Polygandron®+TX, Polyversum®)+TX,Pythium periplocum+TX, Rhanella aquatilis+TX, Rhanella spp.+TX, Rhizobia(Dormal®+TX, Vault®)+TX, Rhizoctonia+TX, Rhodococcus globerulus strainAQ719+TX, Rhodosporidium diobovatum+TX, Rhodosporidium toruloides+TX,Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX,Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomycescerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor+TX, Sclerotiniaminor (SARRITOR®)+TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX,Spodoptera exigua nuclear polyhedrosis virus (Spod-X®+TX, Spexit®)+TX,Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX,Sordaria fimicola+TX, Spodoptera littoralis nucleopolyhedrovirus(Littovir®)+TX, Sporobolomyces roseus+TX, Stenotrophomonasmaltophilia+TX, Streptomyces ahygroscopicus+TX, Streptomycesalbaduncus+TX, Streptomyces exfoliates+TX, Streptomyces galbus+TX,Streptomyces griseoplanus+TX, Streptomyces griseoviridis (Mycostop®)+TX,Streptomyces lydicus (Actinovate®)+TX, Streptomyces lydicus WYEC-108(ActinoGrow®)+TX, Streptomyces violaceus+TX, Tilletiopsis minor+TX,Tilletiopsis spp.+TX, Trichoderma asperellum (T34 Biocontrol®)+TX,Trichoderma gamsii (Tenet®)+TX, Trichoderma atroviride (Plantmate®)+TX,Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai(Mycostar®)+TX, Trichoderma harzianum T-22 (Trianum-P®+TX, PlantShieldHC®+TX, RootShield®+TX, Trianum-G®)+TX, Trichoderma harzianum T-39(Trichodex®)+TX, Trichoderma inhamatum+TX, Trichoderma koningii+TX,Trichoderma spp. LC 52 (Sentinel®)+TX, Trichoderma lignorum+TX,Trichoderma longibrachiatum+TX, Trichoderma polysporum (Binab T®)+TX,Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerlyGliocladium virens GL-21) (SoilGuard®)+TX, Trichoderma viride+TX,Trichoderma viride strain ICC 080 (Remedier®)+TX, Trichosporonpullulans+TX, Trichosporon spp.+TX, Trichothecium spp.+TX, Trichotheciumroseum+TX, Typhula phacorrhiza strain 94670+TX, Typhula phacorrhizastrain 94671+TX, Ulocladium atrum+TX, Ulocladium oudemansii(Botry-Zen®)+TX, Ustilago maydis+TX, various bacteria and supplementarymicronutrients (Natural II®)+TX, various fungi (MillenniumMicrobes®)+TX, Verticillium chlamydosporium+TX, Verticillium lecanii(Mycotal®+TX, Vertalec®)+TX, Vip3Aa20 (VIPtera®)+TX, Virgibaclillusmarismortui+TX, Xanthomonas campestris pv. Poae (Camperico®)+TX,Xenorhabdus bovienii+TX, Xenorhabdus nematophilus; and

Plant extracts including: pine oil (Retenol®)+TX, azadirachtin (PlasmaNeem Oil®+TX, AzaGuard®+TX, MeemAzal®+TX, Molt-X®+TX, Botanical IGR(Neemazad®+TX, Neemix®)+TX, canola oil (Lilly Miller Vegol®)+TX,Chenopodium ambrosioides near ambrosioides (Requiem®)+TX, Chrysanthemumextract (Crisant®)+TX, extract of neem oil (Trilogy®)+TX, essentialsoils of Labiatae (Botania®)+TX, extracts of clove rosemary peppermintand thyme oil (Garden insect killer®)+TX, Glycinebetaine(Greenstim®)+TX, garlic+TX, lemongrass oil (GreenMatch®)+TX, neemoil+TX, Nepeta cataria (Catnip oil)+TX, Nepeta catarina+TX, nicotine+TX,oregano oil (MossBuster®)+TX, Pedaliaceae oil (Nematon®)+TX,pyrethrum+TX, Quillaja saponaria (NemaQ®)+TX, Reynoutria sachalinensis(Regalia®+TX, Sakalia®)+TX, rotenone (Eco Roten®)+TX, Rutaceae plantextract (Soleo®)+TX, soybean oil (Ortho ecosense®)+TX, tea tree oil(Timorex Gold®)+TX, thymus oil+TX, AGNIQUE® MMF+TX, BugOil®+TX, mixtureof rosemary sesame pepermint thyme and cinnamon extracts (EF 300®)+TX,mixture of clove rosemary and peppermint extract (EF 400®)+TX, mixtureof clove pepermint garlic oil and mint (Soil Shot®)+TX, kaolin(Screen®)+TX, storage glucam of brown algae (Laminarin®); and

pheromones including: blackheaded fireworm pheromone (3M SprayableBlackheaded Fireworm Pheromone®)+TX, Codling Moth Pheromone (Paramountdispenser-(CM)/Isomate C-Plus®)+TX, Grape Berry Moth Pheromone (3MMEC-GBM Sprayable Pheromone®)+TX, Leafroller pheromone (3M MEC—LRSprayable Pheromone®)+TX, Muscamone (Snip7 Fly Bait®+TX, Starbar PremiumFly Bait®)+TX, Oriental Fruit Moth Pheromone (3M oriental fruit mothsprayable pheromone®)+TX, Peachtree Borer Pheromone (Isomate-P®)+TX,Tomato Pinworm Pheromone (3M Sprayable pheromone®)+TX, Entostat powder(extract from palm tree) (Exosex CM®)+TX, (E+TX,Z+TX,Z)-3+TX,8+TX,11Tetradecatrienyl acetate+TX,(Z+TX,Z+TX,E)-7+TX,11+TX,13-Hexadecatrienal+TX,(E+TX,Z)-7+TX,9-Dodecadien-1-yl acetate+TX, 2-Methyl-1-butanol+TX,Calcium acetate+TX, Scenturion®+TX, Biolure®+TX, Check-Mate®+TX,Lavandulyl senecioate; and

Macrobials including: Aphelinus abdominalis+TX, Aphidius ervi(Aphelinus-System®)+TX, Acerophagus papaya+TX, Adalia bipunctata(Adalia-System®)+TX, Adalia bipunctata (Adaline®)+TX, Adalia bipunctata(Aphidalia®)+TX, Ageniaspis citricola+TX, Ageniaspis fuscicollis+TX,Amblyseius andersoni (Anderline®+TX, Andersoni-System®)+TX, Amblyseiuscalifornicus (Amblyline®+TX, Spical®)+TX, Amblyseius cucumeris(Thripex®+TX, Bugline cucumeris®)+TX, Amblyseius fallacis(Fallacis®)+TX, Amblyseius swirskii (Bugline swirskii®+TX,Swirskii-Mite®)+TX, Amblyseius womersleyi (WomerMite®)+TX, Amitushesperidum+TX, Anagrus atomus+TX, Anagyrus fusciventris+TX, Anagyruskamali+TX, Anagyrus loecki+TX, Anagyrus pseudococci (Citripar®)+TX,Anicetus benefices+TX, Anisopteromalus calandrae+TX, Anthocorisnemoralis (Anthocoris-System®)+TX, Aphelinus abdominalis (Apheline®+TX,Aphiline®)+TX, Aphelinus asychis+TX, Aphidius colemani (Aphipar®)+TX,Aphidius ervi (Ervipar®)+TX, Aphidius gifuensis+TX, Aphidius matricariae(Aphipar-M®)+TX, Aphidoletes aphidimyza (Aphidend®)+TX, Aphidoletesaphidimyza (Aphidoline®)+TX, Aphytis lingnanensis+TX, Aphytismelinus+TX, Aprostocetus hagenowii+TX, Atheta coriaria (Staphyline®)+TX,Bombus spp.+TX, Bombus terrestris (Natupol Beehive®)+TX, Bombusterrestris (Beeline®+TX, Tripol®)+TX, Cephalonomia stephanoderis+TX,Chilocorus nigritus+TX, Chrysoperla carnea (Chrysoline®)+TX, Chrysoperlacarnea (Chrysopa®)+TX, Chrysoperla rufilabris+TX, Cirrospilusingenuus+TX, Cirrospilus quadristriatus+TX, Citrostichusphyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus spp.+TX,Coccidoxenoides perminutus (Planopar®)+TX, Coccophagus cowperi+TX,Coccophagus lycimnia+TX, Cotesia flavipes+TX, Cotesia plutellae+TX,Cryptolaemus montrouzieri (Cryptobug®+TX, Cryptoline®)+TX, Cybocephalusnipponicus+TX, Dacnusa sibirica+TX, Dacnusa sibirica (Minusa®)+TX,Diglyphus isaea (Diminex®)+TX, Delphastus catalinae (Delphastus®)+TX,Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Diachasmimorphalongicaudata+TX, Diaparsis jucunda+TX, Diaphorencyrtus aligarhensis+TX,Diglyphus isaea+TX, Diglyphus isaea (Miglyphus®+TX, Digline®)+TX,Dacnusa sibirica (DacDigline®+TX, Minex®)+TX, Diversinervus spp.+TX,Encarsia citrina+TX, Encarsia formosa (Encarsia max®+TX, Encarline®+TX,En-Strip®)+TX, Eretmocerus eremicus (Enermix®)+TX, Encarsiaguadeloupae+TX, Encarsia haitiensis+TX, Episyrphus balteatus(Syrphidend®)+TX, Eretmoceris siphonini+TX, Eretmocerus califomicus+TX,Eretmocerus eremicus (Ercal®+TX, Eretline e®)+TX, Eretmocerus eremicus(Bemimix®)+TX, Eretmocerus hayati+TX, Eretmocerus mundus (Bemipar®+TX,Eretline m®)+TX, Eretmocerus siphonini+TX, Exochomusquadripustulatus+TX, Feltiella acarisuga (Spidend®)+TX, Feltiellaacarisuga (Feltiline®)+TX, Fopius arisanus+TX, Fopius ceratitivorus+TX,Formononetin (Wirless Beehome®)+TX, Franklinothrips vespiformis(Vespop®)+TX, Galendromus occidentalis+TX, Goniozus legneri+TX,Habrobracon hebetor+TX, Harmonia axyridis (HarmoBeetle®)+TX,Heterorhabditis spp. (Lawn Patrol®)+TX, Heterorhabditis bacteriophora(NemaShield HB®+TX, Nemaseek®+TX, Terranem-Nam®+TX, Terranem®+TX,Larvanem®+TX, B-Green®+TX, NemAttack®+TX, Nematop®)+TX, Heterorhabditismegidis (Nemasys H®+TX, BioNem H®+TX, Exhibitline hm®+TX,Larvanem-M®)+TX, Hippodamia convergens+TX, Hypoaspis aculeifer(Aculeifer-System®+TX, Entomite-A®)+TX, Hypoaspis miles (Hypoline m®+TX,Entomite-M®)+TX, Lbalia leucospoides+TX, Lecanoideus floccissimus+TX,Lemophagus errabundus+TX, Leptomastidea abnormis+TX, Leptomastixdactylopii (Leptopar®)+TX, Leptomastix epona+TX, Lindorus lophanthae+TX,Lipolexis oregmae+TX, Lucilia caesar (Natufly®)+TX, Lysiphlebustestaceipes+TX, Macrolophus caliginosus (Mirical-N®+TX, Macroline c®+TX,Mirical®)+TX, Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycuslounsburyi+TX, Micromus angulatus (Milacewing®)+TX, Microterysflavus+TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®)+TX,Neodryinus typhlocybae+TX, Neoseiulus californicus+TX, Neoseiuluscucumeris (THRYPEX®)+TX, Neoseiulus fallacis+TX, Nesideocoris tenuis(NesidioBug®+TX, Nesibug®)+TX, Ophyra aenescens (Biofly®)+TX, Oriusinsidiosus (Thripor-I®+TX, Online i®)+TX, Orius laevigatus(Thripor-L®+TX, Oriline I®)+TX, Orius majusculus (Oriline m®)+TX, Oriusstrigicoffis (Thripor-S®)+TX, Pauesia juniperorum+TX, Pediobiusfoveolatus+TX, Phasmarhabditis hermaphrodita (Nemaslug®)+TX,Phymastichus coffee+TX, Phytoseiulus macropilus+TX, Phytoseiuluspersimilis (Spidex®+TX, Phytoline p®)+TX, Podisus maculiventris(Podisus®)+TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX,Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastixmexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX,Quadrastichus spp.+TX, Rhyzobius lophanthae+TX, Rodolia cardinalis+TX,Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion avenae(Ervibank®)+TX, Steinernema carpocapsae (Nematac C®+TX, Millenium®+TX,BioNem C®+TX, NemAttack®+TX, Nemastar®+TX, Capsanem®)+TX, Steinernemafeltiae (NemaShield®+TX, Nemasys F®+TX, BioNem F®+TX,Steinernema-System®+TX, NemAttack®+TX, Nemaplus®+TX, Exhibitline sf®+TX,Scia-rid®+TX, Entonem®)+TX, Steinernema kraussei (Nemasys L®+TX, BioNemL®+TX, Exhibitline srb®)+TX, Steinernema riobrave (BioVector®+TX,BioVektor®)+TX, Steinernema scapterisci (Nematac S®)+TX, Steinernemaspp.+TX, Steinernematid spp. (Guardian Nematodes®)+TX, Stethoruspunctillum (Stethorus®)+TX, Tamarixia radiate+TX, Tetrastichussetifer+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Trichogrammabrassicae (Tricholine b®)+TX, Trichogramma brassicae (Tricho-Strip®)+TX,Trichogramma evanescens+TX, Trichogramma minutum+TX, Trichogrammaostriniae+TX, Trichogramma platneri+TX, Trichogramma pretiosum+TX,Xanthopimpla stemmator; and

other biologicals including: abscisic acid+TX, bioSea®+TX,Chondrostereum purpureum (Chontrol Paste®)+TX, Colletotrichumgloeosporioides (Collego®)+TX, Copper Octanoate (Cueva®)+TX, Delta traps(Trapline d®)+TX, Erwinia amylovora (Harpin) (ProAct®+TX, Ni-HIBIT GoldCST®)+TX, Ferri-phosphate (Ferramol®)+TX, Funnel traps (Trapline y®)+TX,Gallex®+TX, Growers Secret®+TX, Homo-brassonolide+TX, Iron Phosphate(Lilly Miller Worry Free Ferramol Slug & Snail Bait®)+TX, MCP hail trap(Trapline f®)+TX, Microctonus hyperodae+TX, Mycoleptodiscus terrestris(Des-X®)+TX, BioGain®+TX, Aminomite®+TX, Zenox®+TX, Pheromone trap(Thripline ams®)+TX, potassium bicarbonate (MilStop®)+TX, potassiumsalts of fatty acids (Sanova®)+TX, potassium silicate solution(Sil-Matrix®)+TX, potassium iodide+potassium thiocyanate (Enzicur®)+TX,SuffOil-X®+TX, Spider venom+TX, Nosema locustae (Semaspore OrganicGrasshopper Control®)+TX, Sticky traps (Trapline YF®+TX, RebellAmarillo®)+TX and Traps (Takitrapline y+b®)+TX.

The references in brackets behind the active ingredients, e.g.[3878-19-1] refer to the Chemical Abstracts Registry number. The abovedescribed mixing partners are known. Where the active ingredients areincluded in “The Pesticide Manual” [The Pesticide Manual—A WorldCompendium; Thirteenth Edition; Editor: C. D. S. TomLin; The BritishCrop Protection Council], they are described therein under the entrynumber given in round brackets hereinabove for the particular compound;for example, the compound “abamectin” is described under entry number(1). Where “[CCN]” is added hereinabove to the particular compound, thecompound in question is included in the “Compendium of Pesticide CommonNames”, which is accessible on the internet [A. Wood; Compendium ofPesticide Common Names, Copyright© 1995-2004]; for example, the compound“acetoprole” is described under the internet addresshttp://www.alanwood.net/pesticides/acetoprote.html.

Most of the active ingredients described above are referred tohereinabove by a so-called “common name”, the relevant “ISO common name”or another “common name” being used in individual cases. If thedesignation is not a “common name”, the nature of the designation usedinstead is given in round brackets for the particular compound; in thatcase, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemicalname”, a “traditional name”, a “compound name” or a “development code”is used. CAS Reg. No” means the Chemical Abstracts Registry Number.

The active ingredient mixture of the compounds of formula I selectedfrom Tables 1 to 88 and P with active ingredients described abovecomprises a compound selected from Tables 1 to 88 and P and an activeingredient as described above preferably in a mixing ratio of from 100:1to 1:6000, especially from 50:1 to 1:50, more especially in a ratio offrom 20:1 to 1:20, even more especially from 10:1 to 1:10, veryespecially from 5:1 and 1:5, special preference being given to a ratioof from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewisepreferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4,or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5,or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75,or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750,or 2:750, or 4:750. Those mixing ratios are by weight.

The mixtures as described above can be used in a method for controllingpests, which comprises applying a composition comprising a mixture asdescribed above to the pests or their environment, with the exception ofa method for treatment of the human or animal body by surgery or therapyand diagnostic methods practised on the human or animal body.

The mixtures comprising a compound of formula I selected from Tables 1to 88 and P and one or more active ingredients as described above can beapplied, for example, in a single “ready-mix” form, in a combined spraymixture composed from separate formulations of the single activeingredient components, such as a “tank-mix”, and in a combined use ofthe single active ingredients when applied in a sequential manner, i.e.one after the other with a reasonably short period, such as a few hoursor days. The order of applying the compounds of formula I selected fromTables 1 to 88 and P and the active ingredients as described above isnot essential for working the present invention.

The compositions according to the invention can also comprise furthersolid or liquid auxiliaries, such as stabilizers, for exampleunepoxidized or epoxidized vegetable oils (for example epoxidizedcoconut oil, rapeseed oil or soya oil), antifoams, for example siliconeoil, preservatives, viscosity regulators, binders and/or tackifiers,fertilizers or other active ingredients for achieving specific effects,for example bactericides, fungicides, nematocides, plant activators,molluscicides or herbicides.

The compositions according to the invention are prepared in a mannerknown per se, in the absence of auxiliaries for example by grinding,screening and/or compressing a solid active ingredient and in thepresence of at least one auxiliary for example by intimately mixingand/or grinding the active ingredient with the auxiliary (auxiliaries).These processes for the preparation of the compositions and the use ofthe compounds I for the preparation of these compositions are also asubject of the invention.

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient. The rate of application perhectare is generally 1 to 2000 g of active ingredient per hectare, inparticular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

A preferred method of application in the field of crop protection isapplication to the foliage of the plants (foliar application), it beingpossible to select frequency and rate of application to match the dangerof infestation with the pest in question. Alternatively, the activeingredient can reach the plants via the root system (systemic action),by drenching the locus of the plants with a liquid composition or byincorporating the active ingredient in solid form into the locus of theplants, for example into the soil, for example in the form of granules(soil application). In the case of paddy rice crops, such granules canbe metered into the flooded paddy-field.

The compounds of the invention and compositions thereof are also besuitable for the protection of plant propagation material, for exampleseeds, such as fruit, tubers or kernels, or nursery plants, againstpests of the abovementioned type. The propagation material can betreated with the compound prior to planting, for example seed can betreated prior to sowing. Alternatively, the compound can be applied toseed kernels (coating), either by soaking the kernels in a liquidcomposition or by applying a layer of a solid composition. It is alsopossible to apply the compositions when the propagation material isplanted to the site of application, for example into the seed furrowduring drilling. These treatment methods for plant propagation materialand the plant propagation material thus treated are further subjects ofthe invention. Typical treatment rates would depend on the plant andpest/fungi to be controlled and are generally between 1 to 200 grams per100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds,such as between 10 to 100 grams per 100 kg of seeds.

The term seed embraces seeds and plant propagules of all kinds includingbut not limited to true seeds, seed pieces, suckers, corns, bulbs,fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like andmeans in a preferred embodiment true seeds.

The present invention also comprises seeds coated or treated with orcontaining a compound of formula I. The term “coated or treated withand/or containing” generally signifies that the active ingredient is forthe most part on the surface of the seed at the time of application,although a greater or lesser part of the ingredient may penetrate intothe seed material, depending on the method of application. When the saidseed product is (re)planted, it may absorb the active ingredient. In anembodiment, the present invention makes available a plant propagationmaterial adhered thereto with a compound of formula (I). Further, it ishereby made available, a composition comprising a plant propagationmaterial treated with a compound of formula (I).

Seed treatment comprises all suitable seed treatment techniques known inthe art, such as seed dressing, seed coating, seed dusting, seed soakingand seed pelleting. The seed treatment application of the compoundformula (I) can be carried out by any known methods, such as spraying orby dusting the seeds before sowing or during the sowing/planting of theseeds.

BIOLOGICAL EXAMPLES Example B1 Bemisia tabaci (Cotton White Fly):Feeding/Contact Activity

Cotton leaf discs were placed on agar in 24-well microtiter plates andsprayed with aqueous test solutions prepared from 10'000 ppm DMSO stocksolutions. After drying the leaf discs were infested with adult whiteflies. The samples were checked for mortality 6 days after incubation.The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm: P9, P13 and P14.

Example B2 Diabrotica balteata (Corn Root Worm)

Maize sprouts placed onto an agar layer in 24-well microtiter plateswere treated with aqueous test solutions prepared from 10'000 ppm DMSOstock solutions by spraying. After drying, the plates were infested withL2 larvae (6 to 10 per well). The samples were assessed for mortalityand growth inhibition in comparison to untreated samples 4 days afterinfestation. The following compounds gave an effect of at least 80% inat least one of the two categories (mortality or growth inhibition) atan application rate of 200 ppm: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10,P11, P12, P13, P14, and P15.

Example B3 Euschistus heros (Neotropical Brown Stink Bud)

Soybean leaves on agar in 24-well microtiter plates were sprayed withaqueous test solutions prepared from 10'000 ppm DMSO stock solutions.After drying the leaves were infested with N2 nymphs. The samples wereassessed for mortality and growth inhibition in comparison to untreatedsamples 5 days after infestation. The following compounds gave an effectof at least 80% in at least one of the two categories (mortality orgrowth inhibition) at an application rate of 200 ppm:

P1, P3, P8, P9, P10, P13, P14, and P15

Example B4 Myzus persicae (Green Peach Aphid): Feeding/Contact Activity

Sunflower leaf discs were placed onto agar in a 24-well microtiter plateand sprayed with aqueous test solutions prepared from 10'000 ppm DMSOstock solutions. After drying, the leaf discs were infested with anaphid population of mixed ages. The samples were assessed for mortality6 days after infestation. The following compounds resulted in at least80% mortality at an application rate of 200 ppm: P10, P13, P14 and P15.

Example B5 Myzus persicae (Green Peach Aphid). Systemic Activity

Roots of pea seedlings infested with an aphid population of mixed ageswere placed directly into aqueous test solutions prepared from 10'000DMSO stock solutions. The samples were assessed for mortality 6 daysafter placing seedlings into test solutions. The following compoundresulted in at least 80% mortality at a test rate of 24 ppm: P10.

Example B6 Plutella xylostella (Diamond Back Moth)

24-well microtiter plates with artificial diet were treated with aqueoustest solutions prepared from 10'000 ppm DMSO stock solutions bypipetting. After drying, the plates were infested with L2 larvae (10 to15 per well). The samples were assessed for mortality and growthinhibition in comparison to untreated samples 5 days after infestation.The following compounds gave an effect of at least 80% in at least oneof the two categories (mortality or growth inhibition) at an applicationrate of 200 ppm: P1, P2, P3, P4, P6, P8, P9, P10, P11, P12, P13, P14 andP15.

Example B7 Spodoptera littoralis (Egyptian Cotton Leaf Worm)

Cotton leaf discs were placed onto agar in 24-well microtiter plates andsprayed with aqueous test solutions prepared from 10'000 ppm DMSO stocksolutions. After drying the leaf discs were infested with five L1larvae. The samples were assessed for mortality, anti-feeding effect,and growth inhibition in comparison to untreated samples 3 days afterinfestation. Control of Spodoptera littoralis by a test sample is givenwhen at least one of the categories mortality, anti-feedant effect, andgrowth inhibition is higher than the untreated sample. The followingcompounds resulted in at least 80% control at an application rate of 200ppm: P1, P2, P3, P4, P5, P6, P8, P9, P10, P11, P12, P13, P14, and P15.

Example B8 Spodoptera littoralis (Egyptian Cotton Leaf Worm) SystemicActivity

Test compounds were applied by pipette from 10'000 ppm DMSO stocksolutions into 24-well plates and mixed with agar. Lettuce seeds wereplaced onto the agar and the multi well plate was closed by anotherplate which contained also agar. After 7 days the compound was absorbedby the roots and the lettuce grew into the lid plate. The lettuce leaveswere then cut off into the lid plate. Spodoptera eggs were pipettedthrough a plastic stencil onto a humid gel blotting paper and the lidplate was closed with it. The samples were assessed for mortality,anti-feedant effect and growth inhibition in comparison to untreatedsamples 6 days after infestation. The following compounds gave an effectof at least 80% in at least one of the three categories (mortality,anti-feeding, or growth inhibition) at a test rate of 12.5 ppm:

P10, P13, P14 and P15.

Example B9 Tetranychus urticae (Two-Spotted Spider Mite):Feeding/Contact Activity

Bean leaf discs on agar in 24-well microtiter plates were sprayed withaqueous test solutions prepared from 10'000 ppm DMSO stock solutions.After drying the leaf discs were infested with a mite population ofmixed ages. The samples were assessed for mortality on mixed population(mobile stages) 8 days after infestation. The following compoundsresulted in at least 80% mortality at an application rate of 200 ppm:P10 and P13.

Example B10 Thrips tabaci (Onion Thrips) Feeding/Contact Activity

Sunflower leaf discs were placed on agar in 24-well microtiter platesand sprayed with aqueous test solutions prepared from 10'000 ppm DMSOstock solutions. After drying the leaf discs were infested with a thripspopulation of mixed ages. The samples were assessed for mortality 6 daysafter infestation. The following compounds resulted in at least 80%mortality at an application rate of 200 ppm: P3 and P10.

Example B11 Aedes aegypti (Yellow Fever Mosquito):

Test solutions, at an application rate of 200 ppm in ethanol, wereapplied to 12 well tissue culture plates. Once the deposits were dry,five, two to five day old adult female Aedes aegypti were added to eachwell, and sustained with a 10% sucrose solution in a cotton wool plug.Assessment of knockdown was made one hour after introduction, andmortality was assessed at 24 and 48 hours after introduction. Thefollowing compounds gave at least 80% control of Aedes aegypti after 48h and/or 24 h: P9, P10, P11, P13, P14 and P15.

Example B12 Anopheles stephensi (Indian Malaria Mosquito):

Test solutions, at an application rate of 200 ppm in ethanol, wereapplied to 12 well tissue culture plates. Once the deposits were dry,five, two to five day old adult female Anopheles stephensi were added toeach well, and sustained with a 10% sucrose solution in a cotton woolplug. Assessment of knockdown was made one hour after introduction, andmortality was assessed at 24 and 48 hours after introduction. Thefollowing compounds gave at least 80% control of Anopheles stephensiafter 48 h and/or 24 h: P10 and P13.

Comparative Example

Prior art compound: Compound V12.03 described on page 196 of WO2015/000715:

Compounds of this Invention:

The compounds V12.03, P1 and P3 are structurally identical except forthe substitution pattern at the pyridine moiety. The pyridine moiety ofthe prior art compound V12.03 is unsubstituted, the compounds P1 and P3of this invention are substituted by a pyrazole and phenyl grouprespectively at the 6-position of the pyridine ring. The pyrazole groupis substituted by trifluoromethyl and the phenyl group is substituted bychloro.

Example B13

Insecticidal action against Diabrotica balteata (Corn root worm),Plutella xylostella (Diamond black moth), and Spodoptera littoralis(Egyptian cotton leaf worm). The tests were carried out as described inbiological examples B2, B6 and B7, respectively, with the larvalfeeding/contact activity being reported as Breakpoint (BP₈₀) values inparts per million (i.e. the lowest concentration which gives 80% larvalmortality).

TABLE B13 Insecticidal action against Diabrotica balteata (Corn rootworm), Plutella xylostella (Diamond black moth), and Spodopteralittoralis (Egyptian cotton leaf worm). BP₈₀ Values in ppm CompoundDiabrotica Plutella Spodoptera No. Compound balteata xylostellalittoralis V12.03

16 250 250 P1

3 12 12 P3

0.8 12 0.8

As is evident from Table B13, the compounds P1 and P3 according to thisinvention show a superior insecticidal action against Diabroticabalteata (Corn root worm), Plutella xylostella (Diamond black moth), andSpodoptera littoralis (Egyptian cotton leaf worm) compared to compoundV12.03 of the prior art.

This surprising enhancement of insecticidal activity was not to beexpected in view of the close structural similarity of these compounds.

Example B14 Comparison of the Insecticidal Activity of Compounds of thisInvention with the Prior Art

In order to demonstrate the surprising increase in insecticidal activityin comparison with the prior art, the insecticidal activity of thefollowing compounds have been tested:

Prior art compound: Compound V12.01 described on page 196 of WO2015/000715:

Compounds of this Invention:

The compounds V12.01, P4 and P5 are structurally identical except forthe substitution pattern at the pyridine moiety. The pyridine moiety ofthe prior art compound V12.03 is unsubstituted at the 6-position, thecompounds P1 and P3 of this invention are substituted by a phenyl moietyat the 6-position of the pyridine moiety. The phenyl moiety issubstituted by trifluoromethyl at the 3- and 4-position respectively. Inall three compounds, the 5-position of the pyridine moiety issubstituted by trifluoromethyl.

Example B14

Insecticidal action against Diabrotica balteata (Corn root worm). Thetest were carried out as described in biological example B6 with thelarval feeding contact activity being reported as Breakpoint (BP₈₀)values in parts per million (i.e. the lowest concentration which gives80% larval mortality).

TABLE B14 Insecticidal action against Diabrotica balteata (Corn rootworm). BP₈₀ Values in ppm Compound Diabrotica No. Compound balteataV12.01

16 P4

10 P5

10

Table B14: Insecticidal Action Against

As is evident from Table B14, the compounds P4 and P5 according to thisinvention show a superior insecticidal action against Diabroticabalteata (Corn root worm) compared to compound V12.01 of the prior art.

This surprising enhancement of insecticidal activity was not to beexpected in view of the close structural similarity of these compounds.

1. A method comprising: reacting a compound of Formula (II),

wherein Xb₁ is a leaving group, boron derived functional group, ortrialkyl tin derivative; A represents CH, N or the N-oxide; A₁ is CH, Nor the N-oxide; X is S, SO or SO₂; R₁ is C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl; or R₁ isC₃-C₈cycloalkyl-C₁-C₄alkyl mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano and C₁-C₄alkyl; orR₁ is C₂-C₈alkenyl, C₂-C₆haloalkenyl or C₂-C₈alkynyl; R₂ is halogen,cyano, C₁-C₈haloalkyl or C₁-C₈haloalkyl substituted by one or twosubstituents selected from the group consisting of hydroxyl, methoxy andcyano; R₂ is C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), or —C(O)C₁-C₄haloalkyl; or R₂is C₃-C₈cycloalkyl which can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano and C₁-C₄alkyl; X₁is NR₅, wherein R₅ is hydrogen, C₁-C₄alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,C₁-C₄alkoxy-C₁-C₄alkyl or C₃-C₆cycloalkyl; or X₁ is oxygen or sulfur; R₃is hydrogen or C₁-C₂-alkyl; and R₄ is hydrogen, halogen orC₁-C₃haloalkyl, with Yb₁-Q, Yb₂-Q, or a Q which contains an appropriateNH functionality, wherein Yb₁ is a boron-derived functional group orleaving group; Yb₂ is a trialkyl tin derivative or leaving group; and Qis phenyl which can be mono- or polysubstituted by substituents selectedfrom the group consisting of halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl;or Q is a five- to ten-membered monocyclic or fused bicyclic ring systemlinked via a carbon atom to the ring which contains the group A, saidring system can be aromatic, partially saturated or fully saturated andcontains 1 to 4 hetero atoms selected from the group consisting ofnitrogen, oxygen and sulfur, with the proviso that each ring systemcannot contain more than 2 oxygen atoms and more than 2 sulfur atoms,said five- to ten-membered ring system can be mono- to polysubstitutedby substituents independently selected from the group consisting ofhalogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl; or Q is a five- tosix-membered, aromatic, partially saturated or fully saturated ringsystem linked via a nitrogen atom to the ring which contains the groupA, said ring system contains 1, 2 or 3 heteroatoms selected from thegroup consisting of nitrogen, oxygen and sulphur, with the proviso thatsaid ring system cannot contain more than one oxygen atom and more thanone sulfur atom and can be mono- or polysubstituted by substituentsselected from the group consisting of halogen, cyano, C₁-C₄alkyl,C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄alkylsulfanyl,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, —C(O)C₁-C₄alkyl,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyland —C(O)C₁-C₄haloalkyl; Q is C₃-C₆cycloalkyl, or C₃-C₆cycloalkyl mono-or polysubstituted by substituents selected from the group consisting ofhalogen, cyano, CONH₂, carboxyl, C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl and phenyl, wherein said phenyl can be mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄haloalkylsulfanyl, C₁-C₄halo-alkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl; or Q is C₂-C₆alkenyl, orC₂-C₆alkenyl mono- or polysubstituted by substituents selected from thegroup consisting of halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl and phenyl, wherein said phenyl can be mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl; or Q is C₂-C₆alkynyl, orC₂-C₆alkynyl mono- or polysubstituted by substituents selected from thegroup consisting of halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl, tri(C₁-C₄alkyl)silyl and phenyl, wherein said phenylcan be mono- or polysubstituted by substituents selected from the groupconsisting of halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄halo-alkylsulfanyl,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl;or Q is C₁-C₆alkyl, or C₁-C₆alkyl mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl, tri(C₁-C₄alkyl)silyl andphenyl, wherein said phenyl can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄halo-alkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyland —C(O)C₁-C₄haloalkyl; to form a compound of formula (I)

wherein R₁, R₂, R₃, R₄, A, A₁, X, X₁, and Q are as defined above; withthe proviso that: when Xb₁ is a leaving group, Yb₁ is a boron-derivedfunctional group and Yb₂ is a trialkyl tin derivative; and when X_(b1)is a boron derived functional group or trialkyl tin derivative, Yb₁ andYb₂ are leaving groups or the reacting is not with the Q which containsan appropriate NH functionality.
 2. The method of claim 1, wherein thereacting is with Yb₁-Q.
 3. The method of claim 2, wherein Yb₁ is B(OH)₂or B(OR_(b1))₂, wherein R_(b1), is a C₁-C₄alkyl group or the two groupsOR_(b1) form together with the boron atom a five membered ring.
 4. Themethod of claim 3, wherein reacting further comprises the presence of apalladium based catalyst, a base, and a solvent.
 5. The method of claim3, wherein the reacting is a Suzuki Reaction.
 6. The method of claim 1,wherein the reacting is with Yb₂-Q.
 7. The method of claim 6, whereinYb₂ is tri-n-butyl tin.
 8. The method of claim 7, wherein the reactingfurther comprises the presence of a palladium catalyst and inertsolvent.
 9. The method of claim 7, wherein the reacting is a StilleReaction.
 10. The method of claim 1, wherein the reacting is with Qwhich contains an appropriate NH functionality.
 11. The method of claim10, wherein the reacting is in the presence of a base.
 12. The method ofclaim 11, wherein the reacting is in the presence of a copper catalystand inert solvent.
 13. A method comprising, dehydrating a compound offormula (X) or formula (Xa)

wherein A represents CH, N or the N-oxide; A₁ is CH, N or the N-oxide; Xis S, SO or SO₂; R₁ is C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,C₃-C₆cycloalkyl-C₁-C₄alkyl; or R₁ is C₃-C₆cycloalkyl-C₁-C₄alkyl mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, cyano and C₁-C₄alkyl; or R₁ is C₂-C₆alkenyl, C₂-C₆haloalkenylor C₂-C₆alkynyl; R₂ is halogen, cyano, C₁-C₆haloalkyl or C₁-C₆haloalkylsubstituted by one or two substituents selected from the groupconsisting of hydroxyl, methoxy and cyano; or R₂ isC₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl,O(C₁-C₄haloalkyl), or —C(O)C₁-C₄haloalkyl; or R₂ is C₃-C₆cycloalkylwhich can be mono- or polysubstituted by substituents selected from thegroup consisting of halogen, cyano and C₁-C₄alkyl; R₃ is hydrogen orC₁-C₂-alkyl; and R₄ is hydrogen, halogen or C₁-C₃haloalkyl, R₅ ishydrogen, C₁-C₄alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₁-C₄alkoxy-C₁-C₄alkylor C₃-C₈cycloalkyl; Q is phenyl which can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyland —C(O)C₁-C₄haloalkyl; or Q is a five- to ten-membered monocyclic orfused bicyclic ring system linked via a carbon atom to the ring whichcontains the group A, said ring system can be aromatic, partiallysaturated or fully saturated and contains 1 to 4 hetero atoms selectedfrom the group consisting of nitrogen, oxygen and sulfur, with theproviso that each ring system cannot contain more than 2 oxygen atomsand more than 2 sulfur atoms, said five- to ten-membered ring system canbe mono- to polysubstituted by substituents independently selected fromthe group consisting of halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, —C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl;or Q is a five- to six-membered, aromatic, partially saturated or fullysaturated ring system linked via a nitrogen atom to the ring whichcontains the group A, said ring system contains 1, 2 or 3 heteroatomsselected from the group consisting of nitrogen, oxygen and sulphur, withthe proviso that said ring system cannot contain more than one oxygenatom and more than one sulfur atom and can be mono- or polysubstitutedby substituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄alkylsulfanyl, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,—C(O)C₁-C₄alkyl, C₁-C₄haloalkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl; Q is C₃-C₆cycloalkyl, orC₃-C₆cycloalkyl mono- or polysubstituted by substituents selected fromthe group consisting of halogen, cyano, CONH₂, carboxyl, C₁-C₄alkyl,C₁-C₄haloalkyl, C₃-C₆cycloalkyl and phenyl, wherein said phenyl can bemono- or polysubstituted by substituents selected from the groupconsisting of halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄haloalkylsulfanyl,C₁-C₄halo-alkylsulfinyl, C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl;or Q is C₂-C₆alkenyl, or C₂-C₆alkenyl mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl and phenyl, wherein saidphenyl can be mono- or polysubstituted by substituents selected from thegroup consisting of halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄haloalkoxy, C₁-C₄alkoxy, C₁-C₄haloalkylsulfanyl,C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl;or Q is C₂-C₆alkynyl, or C₂-C₆alkynyl mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl, tri(C₁-C₄alkyl)silyl andphenyl, wherein said phenyl can be mono- or polysubstituted bysubstituents selected from the group consisting of halogen, cyano,C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy, C₁-C₄alkoxy,C₁-C₄halo-alkylsulfanyl, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyland —C(O)C₁-C₄haloalkyl; or Q is C₁-C₆alkyl, or C₁-C₆alkyl mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₃-C₆cycloalkyl,tri(C₁-C₄alkyl)silyl and phenyl, wherein said phenyl can be mono- orpolysubstituted by substituents selected from the group consisting ofhalogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄haloalkoxy,C₁-C₄alkoxy, C₁-C₄halo-alkylsulfanyl, C₁-C₄haloalkylsulfinyl,C₁-C₄haloalkylsulfonyl and —C(O)C₁-C₄haloalkyl; to form a compound offormula (I)

wherein X₁ is N-R₅, and R₁, R₂, R₃, R₄, R₅ A, A₁, X, and Q are asdefined above.